CN107337766B - High-adaptability polycarboxylate superplasticizer and preparation method thereof - Google Patents
High-adaptability polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- 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
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- 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
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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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 a high-adaptability polycarboxylate superplasticizer. The high-adaptability polycarboxylate superplasticizer disclosed by the invention is prepared from the following components in a molar ratio of 1-5: 1: 0.1-0.3: 0.05-0.2 of carboxylic acid monomer A, high molecular weight polyether macromonomer B, functional polycation macromonomer C and unsaturated phosphate ester monomer D. The high-adaptability polycarboxylate superplasticizer is suitable for areas with high sand-aggregate mud content, and has the advantages of low mixing amount, high water reduction and high slump loss resistance; the high-adaptability polycarboxylate superplasticizer disclosed by the invention is simple in preparation process, green and environment-friendly in production process and low in cost.
Description
Technical Field
The invention relates to a high-adaptability polycarboxylate superplasticizer and a preparation method thereof, belonging to the technical field of concrete admixtures.
Background
In recent years, along with the development of concrete technology, the application of the polycarboxylic acid high-performance water reducing agent is increasingly popularized, and the polycarboxylic acid high-performance water reducing agent is gradually and widely applied to various projects due to the advantages of low mixing amount, high water reducing rate, excellent slump retaining performance, low shrinkage, energy conservation, environmental protection and the like. But also exposes some problems, especially the influence of the mud content in the sand and stone on the performance of the polycarboxylate superplasticizer is obvious, thereby causing poor concrete fluidity and large slump loss, and greatly restricting the popularization and application of the polycarboxylate superplasticizer. And domestic building sandstone resources are gradually reduced, some gravels with higher mud content are already used for building materials on a large scale, and the problem that the mud content of the gravels exceeds the standard needs to be solved urgently.
In actual construction, when the mud content of the sandstone aggregate exceeds the standard and the working performance of concrete is influenced, a method for washing the sandstone aggregate is generally adopted, but the method can damage the gradation of sandstone and generate a large amount of sewage to pollute the environment; the adoption of excessive amount of polycarboxylic acid can improve the working performance of the concrete, but obviously increase the cost of the single concrete, and cause the problems of serious concrete segregation, overlong setting time and the like.
As the influence of the mud powder in the sand aggregate on the dispersion performance of the polycarboxylate superplasticizer is very obvious, experts and scholars at home and abroad develop a series of researches on the influence of the mud powder on the performance of the polycarboxylate superplasticizer, and the widely accepted mechanism at present is the adsorption effect of the layered structure of the mud powder on the polycarboxylate superplasticizer. Professor J.Plank in Germany considers that there are both physical and chemical actions between clay and polycarboxylic acid water-reducing agent, wherein the clay adsorbs the water-reducing agent to the surface by physical action and then adsorbs the side chain or the whole body of the water-reducing agent to the interlayer by chemical action, thereby greatly reducing the polycarboxylic acid water-reducing agent which reacts with cement particles, and causing the concrete performance to be obviously reduced. In view of the molecular structure of the polycarboxylate water reducer, the Magarotto teaches that different types of polycarboxylate water reducers containing comb-type side chain structures are very sensitive to mud, because the interlaminar structure of clay minerals in mud powder is matched with the chain linkage of the comb-type side chain structures of the polycarboxylate water reducers, and the polycarboxylate water reducers are mostly intercalated into clay minerals in a chemisorption mode and are not adsorbed on the surfaces of the clay minerals in a charge adsorption mode. The professor Wanglin in China considers that the adsorption of the mud powder and the directional adsorption of the hydrophobic group have the combined action, and the chelation of metal cations adsorbed by the mud powder and the polycarboxylic acid water reducing agent is the mechanism of adsorbing the polycarboxylic acid water reducing agent by the mud powder.
At present, the polycarboxylic acid water reducing agent with high adaptability can be synthesized by the structural design of polycarboxylic acid. The following technical route is generally adopted when synthesizing the high-adaptability polycarboxylate water reducing agent: increasing the size of a side chain, introducing a functional group capable of reducing clay adsorption, synthesizing a poly carboxylic acid without a PEO side chain, reducing the charge density of a main chain of the poly carboxylic acid, prolonging the length of a polyether side chain and the like. The professor of Plank proposes to synthesize a polycarboxylate water reducer without PEO side chains, and acrylic acid and hydroxy ester thereof are directly copolymerized to prepare the anti-clay polycarboxylate water reducer without adopting a macromonomer, so that the anti-clay polycarboxylate water reducer has a good using effect. By introducing an anti-clay group into a branched chain of the polycarboxylate superplasticizer by Xiaofei et al in China, the hydrogen bond effect between an EO group on the branched chain of the polycarboxylate superplasticizer and a clay layer is weakened, and the synthesized polycarboxylate superplasticizer for inhibiting the clay adsorption enables mortar and concrete to have good working performance when the mud content is in a certain range. A clay-resistant polycarboxylate superplasticizer is introduced in Chinese patent CN102923989A, wherein a polyethylene polyamine monomer is used, a polyethylene polyamine chain is mainly adsorbed on the surface of clay particles to play a role in shielding and dispersing, but only the universality of the clay resistance of one type of soil is tested to be tested. Chinese patent CN102358763A discloses an additive for inhibiting side effects of clay, which essentially belongs to a small molecular regulator, but has a limited water-reducing rate, and needs to be compounded with a water-reducing agent in application. However, the compounding method not only greatly increases the cost when solving the problem of the mud content of the aggregate, but also causes the problems of compatibility, storage stability and the like of organic and inorganic components. Chinese patent CN102617811A describes a preparation method of an amphoteric vinyl polymer concrete mud-resistant agent, and then a method of esterification and polymerization is carried out firstly, and a cationic group is introduced into a molecular structure to obtain the mud-resistant agent.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-adaptability polycarboxylate water reducer, which synthesizes polycarboxylate macromolecules with large steric hindrance effect and charge shielding effect to realize the resistance effect on clay minerals, so that the sensitivity of the polycarboxylate water reducer to the content of aggregate mud is reduced, the water reducing effect of the polycarboxylate water reducer is exerted, and the workability and durability of concrete are improved.
From the structure of the polycarboxylate superplasticizer, a hydrophilic PEO side chain of the polycarboxylate superplasticizer is easy to form a hydrogen bond structure with a clay layer, so that the polycarboxylate superplasticizer which reacts with cement particles is greatly reduced, and the performance of concrete is obviously reduced. In consideration of the aspect, an unsaturated monomer containing a polycation macromolecular chain is introduced into the molecular structure of the polycarboxylic acid water reducer, the cationic macromolecular chain structure can adsorb a plurality of clay particles, and an adsorption protective film of an organic cationic polymer is formed on the surfaces of the clay particles, so that the adsorption of the clay to the effective components of the water reducer is effectively prevented, the mud resistance and the adaptability of the polycarboxylic acid water reducer can be greatly improved, and meanwhile, the crystal morphology formed in the initial stage of cement hydrated ettringite can be effectively improved by introducing a phosphate adsorption group, so that the functions of reducing water, retarding and slump retaining are achieved. Thereby greatly reducing the adsorption effect of the clay on the polycarboxylate superplasticizer and improving the adaptability of the polycarboxylate superplasticizer to sandstone aggregates.
The invention provides a high-adaptability polycarboxylate superplasticizer which is prepared from the following components in a molar ratio of 1-5: 1: 0.1-0.3: 0.05-0.2 of carboxylic acid monomer A, high molecular weight polyether macromonomer B, functional polycation macromonomer C and unsaturated phosphate ester monomer D, wherein the free radical copolymerization reaction is carried out to obtain the product, and the product is prepared by the following steps:
the carboxylic acid monomer A has a structure shown in a formula (I):
in the formula, R1Is H or COOM; r2Is H, CH3Or CH2COOM; and when R is1When it is COOM, R2Is not CH at the same time3Or CH2COOM; m is hydrogen atom, alkali metal ion, alkaline earth metal ion, ammonium ion or organic amine group;
the structure of the high molecular weight polyether macromonomer B is shown as the formula (II):
in the formula, R3Is H or CH3；R4H or an alkyl group having 1 to 3 carbon atoms; x1Is CH2、CH2CH2、OCH2CH2Or OCH2CH2CH2CH2(ii) a n is the average addition mole number of polyoxyethylene and is an integer of 25-150;
the structure of the functional polycation macromonomer C is shown as the formula (III):
wherein m is the average addition mole number of the poly (N-isopropylacrylamide), and is an integer of 5-10;
the unsaturated phosphate ester monomer D has a structure shown in a formula (IV):
in the formula, R5Is H or CH3；R6Is CH2CH2Or CH2CH2CH2。
The weight average molecular weight of the high-adaptability polycarboxylate superplasticizer is 20000-60000; if the molecular weight is too low, the initial dispersing ability of the water reducing agent is reduced; if the molecular weight is too high, both the initial dispersing ability and the later slump retaining ability of the water reducing agent are weakened.
According to the high-adaptability polycarboxylate water reducer, the carboxylic acid monomer A is selected from any one of acrylic acid, methacrylic acid, maleic acid, itaconic acid or sodium salt, potassium salt, calcium salt, ammonium salt and organic amine salt thereof;
the macromolecular polyether macromonomer B is selected from any one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, butenyl polyoxyethylene ether, methyl butenyl polyoxyethylene ether, vinyl polyoxyethylene ether and hydroxybutyl vinyl polyoxyethylene ether;
the functional polycationic macromonomer C is selected from maleimide terminated poly (N-isopropylacrylamide);
the unsaturated phosphate ester monomer D is selected from any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The invention also provides a preparation method of the high-adaptability polycarboxylate superplasticizer, which comprises the following steps:
(1) dissolving a high molecular weight polyether macromonomer B and a functional polycation monomer C in a water solvent, stirring and heating to dissolve into an aqueous solution;
(2) mixing and stirring a carboxylic acid monomer A, an unsaturated phosphoric acid monomer D and water uniformly to obtain a mixed aqueous solution;
(3) dropwise adding the mixed aqueous solution obtained in the step (2) into the solution obtained in the step (1) at a constant speed in the presence of an initiator, continuously keeping the temperature at a constant temperature after all the solutions are dropwise added, carrying out free radical copolymerization on monomers in the solution, and adding an alkaline substance into the solution to neutralize the solution until the pH value is about 6-8 after the reaction is finished, thereby obtaining the polycarboxylic acid water reducer;
in the free radical copolymerization reaction in the step (3), the monomers B and C have high molecular weight and low double bond content, so that the double bond polymerization is difficult due to steric effect; in order to improve the conversion rate of the monomers B and C in the polymerization process, the monomers B and C are directly and completely fed in one step before polymerization in a feeding mode;
the initiator in the step (3) is a free radical water-soluble initiator and comprises an oxidation initiator and a redox initiator; the oxidation initiator independently selects an oxidation component as an initiator, and the redox initiator selects a composition of the oxidation component and a reduction component as the initiator; when the initiator is an oxidation initiator, the using amount of the initiator is 0.1-2% of the total mass of the monomers A + B + C + D, when the initiator is a redox initiator, the total using amount of the oxidation component accounts for 0.1-2% of the total mass of the monomers A + B + C + D, and the mass ratio of the oxidation component to the reduction component is 0.4-4: 1;
the oxidizing component in the initiator can be completely fed in one step in the step (1) and mixed with the monomer B and the monomer C, or prepared into an aqueous solution with water and then dripped into the solution in the step (1) with the mixed aqueous solution in the step (2) at a constant speed; the monomer A, the monomer D, a reducing component in the initiator, a chain transfer agent and water form a mixed aqueous solution, and the mixed aqueous solution is added into the solution in the step (1) in a uniform-speed dropwise adding mode after being uniformly stirred;
the mixed aqueous solution in the step (2) also comprises a water-soluble chain transfer agent; the dosage of the chain transfer agent is 0.05-1% of the total mass of the monomers A + B + C + D, and the weight average molecular weight of the prepared polycarboxylic acid water reducing agent is adjusted by a water-soluble chain transfer agent;
in the step (3), the temperature of the free radical copolymerization reaction is 35-85 ℃, and the reaction temperature is mainly related to the decomposition efficiency and half-life period of the used initiator; the dropping time of the mixed aqueous solution is controlled to be 2-5 hours; the dropping time of the initiator oxidizing component solution is prolonged by 0.5 hour compared with that of the monomer solution; in order to improve the conversion rate of the monomer, the temperature needs to be kept continuously after the initiator solution is dripped, and the temperature keeping time is 1-5 h.
According to the preparation method of the high-adaptability polycarboxylate superplasticizer, the oxidation initiator comprises persulfate or a water-soluble azo compound; the redox initiator comprises a composition of persulfate and any one of bisulfite, sulfite, thiosulfate, pyrosulfite or ferrous salt, or a composition of peroxide and any one of sodium formaldehyde sulfoxylate or L-ascorbic acid; the chain transfer agent is a mercaptan chain transfer agent.
According to the preparation method of the high-adaptability polycarboxylate superplasticizer, after the copolymerization reaction in the step (3) is finished, an alkaline substance is further used for neutralizing, so that the storage stability of a product is enhanced; the alkaline substance used comprises hydroxide, oxide or carbonate of monovalent metal and/or divalent metal, ammonium hydroxide, organic amine; the amount of the alkaline substance is used for adjusting the pH value of the reaction product to 6-8.
According to the preparation method of the high-adaptability polycarboxylate water reducer, the oxidation initiator can be selected from potassium persulfate, azobisisobutylamidine hydrochloride and azobisisobutyronitrile;
the redox initiator may be selected from the group consisting of a combination of hydrogen peroxide and L-ascorbic acid, a combination of potassium persulfate and sodium bisulfite, and a combination of hydrogen peroxide and sodium formaldehyde sulfoxylate;
the chain transfer agent can be selected from 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, 3-mercaptopropanol, thioglycolic acid and mercaptoethanol;
the alkaline substance is selected from sodium hydroxide, triethanolamine, potassium hydroxide, and triisopropanolamine.
According to the preparation method of the high-adaptability polycarboxylate superplasticizer, in the step (3), the mass concentration of the carboxylic acid monomer A, the high-molecular polyether macromonomer B, the functional polycation macromonomer C and the unsaturated phosphoric acid monomer D during polymerization is preferably 35-50%. In the free radical copolymerization, the polymerization concentration also has a significant influence on the performance of the additive: the concentration is too low, the water reducing rate is reduced, and the production efficiency is reduced; the concentration is too high, so that gel is easy to generate in the polymerization process, and the material is scrapped.
The invention also provides the application of the high-adaptability polycarboxylate water reducer in concrete preparation, the prepared high-adaptability polycarboxylate water reducer can be directly used, and functional auxiliaries such as a defoaming agent, a retarder, an air entraining agent, a thickening agent and the like can be selectively added according to the actual engineering situation and mixed in a compounding manner to adjust the air content, the setting time and the cohesiveness of the cement-based material and improve the comprehensive performance of the cement-based material.
The mixing amount of the high-adaptability polycarboxylate superplasticizer is 0.1-0.5% of the total weight of the cementing material. If the mixing amount is too low, the dispersing effect on cement is unsatisfactory; if the mixing amount is too high, the bleeding phenomenon is easy to occur, and the economic waste is also caused. The engineer may prefer within this range depending on the actual situation.
The high-adaptability polycarboxylate superplasticizer is suitable for areas with high sand-aggregate mud content, and has the advantages of low mixing amount, high water reduction and high slump loss resistance; the high-adaptability polycarboxylate superplasticizer disclosed by the invention is simple in preparation process, green and environment-friendly in production process and low in cost.
Detailed Description
The present invention will be described in detail with reference to the following examples for better understanding of the contents of the present invention, but the contents of the examples do not limit the scope of the present invention.
The weight average molecular weight and the polymerization conversion rate of the polycarboxylic acid water reducing agent described in the examples were measured by using a high performance gel chromatograph (GPC). Wherein the separation column adopts Shodex SB806+803 two gel chromatographic columns connected in series, the column temperature is 40 ℃, and the mobile phase is 0.1M NaNO3The flow rate of the aqueous solution is 1.0ml/min, and the sample amount is 20 mul of 0.5 percent aqueous solution; a detector: a ShodexRI-71 type refractive index detector; standard curve preparation used polyethylene glycol GPC standards (Sigma-Aldrich, MW 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).
The raw materials used in the synthesis examples and comparative examples are listed in table 1, below:
TABLE 1 Compound numbers in Synthesis examples and comparative examples
| Code number | Name of Compound | Origin of origin |
| A-1 | Acrylic acid | Commercial purchase |
| A-2 | Methacrylic acid | Commercial purchase |
| A-3 | Maleic acid | Commercial purchase |
| A-4 | Itaconic acid | Commercial purchase |
| A-5 | Acrylic acid sodium salt | Commercial purchase |
| B-1 | Allyl polyoxyethylene ether (n ═ 25) | Commercial purchase |
| B-2 | Methylallyl polyoxyethylene ether (n ═ 50) | Commercial purchase |
| B-3 | Butenyl polyoxyethylene ether (n ═ 75) | Commercial purchase |
| B-4 | Methylbutenyl polyoxyethylene ether (n ═ 100) | Commercial purchase |
| B-5 | Ethylene polyoxyethylene ether (n 150 ═ 150) | Commercial purchase |
| B-6 | Hydroxybutyl vinyl polyoxyethylene ether (n ═ 100) | Commercial purchase |
| C-1 | Maleimide-terminated poly (N-isopropylacrylamide) (m ═ 5) | Commercial purchase |
| C-2 | Maleimide-terminated poly (N-isopropylacrylamide) (m ═ 10) | Commercial purchase |
| C-3 | Maleimide-terminated poly (N-isopropylacrylamide) (m ═ 15) | Commercial purchase |
| D-1 | Acrylic acid hydroxyethyl phosphate | Commercial purchase |
| D-2 | Acrylic acid hydroxypropyl phosphate | Commercial purchase |
| D-3 | Hydroxyethyl methacrylate phosphate | Commercial purchase |
| D-4 | Hydroxypropyl methacrylate phosphate | Commercial purchase |
Example 1
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 200.0g of distilled water, 275.0g of monomer B-1 and 20.1g of monomer C-1, and dissolved by heating with stirring. The temperature is raised to 85 ℃, then 18.0g of monomer A-1, 2.6g of monomer D-1, 1.1g of 3-mercaptopropionic acid and 100.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 3 hours. Simultaneously, initiator solution prepared from 110.0g of distilled water and 5.4g of potassium persulfate is dropwise added at a constant speed for 3.5 h. And after all the solution is dripped, continuously keeping the temperature at constant temperature for 3h, then cooling to about 40 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.0, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 43.5%.
Example 2
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 220.0g of distilled water, 275.0g of monomer B-1 and 102.7g of monomer C-2, and dissolved by stirring at elevated temperature. The temperature is raised to 80 ℃, then 21.5g of monomer A-2, 11.3g of monomer D-2, 3.5g of thioglycolic acid and 80.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2.5 h. Simultaneously dropwise adding an initiator aqueous solution prepared from 120.0g of distilled water and 6.15g of azodiisobutyl amidine hydrochloride at a constant speed for 3 h. And continuously keeping the temperature for 3h at constant temperature after all the solution is dripped, then cooling to about 40 ℃, adding triethanolamine to neutralize until the pH value is about 7.0, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 49.2%.
Example 3
220.0g of distilled water, 275.0g of monomer B-1, 48.3g of monomer C-3 and 3.4g of 30% hydrogen peroxide were put in a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at an elevated temperature. The temperature is raised to 35 ℃, then 29.0g of monomer A-3, 11.3g of monomer D-3, 1.76g of mercaptoethanol, 0.92g L-ascorbic acid and 250.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. And after the monomer solution is dropwise added, continuously keeping the temperature at constant temperature for 3h, then cooling to about 30 ℃, adding potassium hydroxide for neutralization until the pH value is about 7.5, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 43.3%.
Example 4
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 220.0g of distilled water, 275.0g of monomer B-1 and 60.3g of monomer C-1, and dissolved by heating with stirring. The temperature is raised to 50 ℃, then 32.5g of monomer A-4, 3.0g of monomer D-4, 2.38g of 2-mercaptopropionic acid, 0.97g of sodium bisulfite and 150.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. Simultaneously, an initiator aqueous solution prepared from 140.0g of distilled water and 3.54g of potassium persulfate is dropwise added at a constant speed for 2.5 h. And after all the solution is dripped, continuously keeping the temperature for 4h at constant temperature, then cooling to about 40 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.5, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 41.5%.
Example 5
220.0g of distilled water, 220.0g of monomer B-2, 13.7g of monomer C-2 and 1.72g of 30% hydrogen peroxide were put into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at an elevated temperature. The temperature is raised to 65 ℃, then 36.0g of monomer A-1, 1.2g of monomer D-4, 1.06g of 3-mercaptopropanol, 0.23g of sodium formaldehyde sulfoxylate and 260.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 3 hours. And after the monomer solution is dropwise added, continuously keeping the temperature for 2h at constant temperature, then cooling to about 40 ℃, adding triisopropanolamine for neutralization until the pH value is about 7.0, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 35.8%.
Example 6
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 220.0g of distilled water, 330.0g of monomer B-3 and 58.0g of monomer C-3, and dissolved by heating with stirring. The temperature is raised to 75 ℃, then 36.0g of monomer A-1, 4.5g of monomer D-3, 1.15g of 2-mercaptopropionic acid and 100.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. Simultaneously, initiator solution prepared from 150.0g of distilled water and 4.32g of potassium persulfate is dropwise added at a constant speed for 2.5 h. And after all the solution is dripped, continuously keeping the temperature at constant temperature for 3h, then cooling to about 40 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.0, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 47.3%.
Example 7
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 220.0g of distilled water, 440.0g of monomer B-4 and 8.1g of monomer C-1, and dissolved by warming with stirring. The temperature is raised to 85 ℃, then 36.0g of monomer A-1, 4.5g of monomer D-2, 1.03g of thioglycolic acid and 100.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. Simultaneously, initiator aqueous solution prepared from 150.0g of distilled water and 3.07g of azobisisobutyronitrile is dripped at a constant speed for 2.5 hours. And continuously keeping the temperature for 3h at constant temperature after all the solution is dripped, then cooling to about 40 ℃, adding triethanolamine to neutralize until the pH value is about 7.0, and obtaining the high-adaptability polycarboxylate superplasticizer with solid content of 48.3%.
Example 8
220.0g of distilled water, 330.0g of monomer B-5, 20.5g of monomer C-2 and 1.13g of 30% hydrogen peroxide were put into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at an elevated temperature. The temperature is raised to 45 ℃, then 18.0g of monomer A-1, 0.5g of monomer D-1, 0.86g of mercaptoethanol, 0.35g L-ascorbic acid and 280.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 3 hours. And after the monomer solution is dropwise added, continuously keeping the temperature at constant temperature for 1.5h, then cooling to about 30 ℃, adding potassium hydroxide for neutralization until the pH value is about 7.5, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 42.5%.
Example 9
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 220.0g of distilled water, 220.0g of monomer B-6 and 19.3g of monomer C-3, and dissolved by warming with stirring. The temperature is raised to 55 ℃, then 7.2g of monomer A-1, 1.1g of monomer D-1, 0.38g of 2-mercaptopropionic acid, 0.78g of sodium bisulfite and 120.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. Simultaneously, initiator aqueous solution prepared by 120.0g of distilled water and 2.83g of potassium persulfate is dropwise added at a constant speed for 2.5 h. And after all the solution is dripped, continuously keeping the temperature for 2h at constant temperature, then cooling to about 40 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.5, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 35.6%.
Example 10
220.0g of distilled water, 275.0g of monomer B-1, 85.6g of monomer C-2 and 1.37g of 30% hydrogen peroxide were put into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at an elevated temperature. The temperature is raised to 55 ℃, 70.5g of monomer A-5, 7.9g of monomer D-1, 0.95g of 3-mercaptopropanol, 0.21g of sodium formaldehyde sulfoxylate and 300.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. And after the monomer solution is dropwise added, continuously keeping the temperature for 2h at constant temperature, then cooling to about 40 ℃, adding triisopropanolamine for neutralization until the pH value is about 7.0, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 46.2%.
Example 11
220.0g of distilled water, 220.0g of monomer B-2, 24.1g of monomer C-1 and 1.02g of 30% hydrogen peroxide were put into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at an elevated temperature. The temperature is raised to 40 ℃, then 34.4g of monomer A-2, 2.1g of monomer D-1, 0.97g of mercaptoethanol, 0.24g L-ascorbic acid and 200.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. And after the monomer solution is dropwise added, continuously keeping the temperature for 2h, then cooling to about 30 ℃, adding potassium hydroxide for neutralization until the pH value is about 7.5, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 40.2%.
Example 12
220.0g of distilled water, 220.0g of monomer B-6, 14.5g of monomer C-3 and 0.91g of 30% hydrogen peroxide were put into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at elevated temperature. The temperature is raised to 45 ℃, then 19.5g of monomer A-4, 0.8g of monomer D-2, 0.69g of mercaptoethanol, 0.32g L-ascorbic acid and 225.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. And after the monomer solution is dropwise added, continuously keeping the temperature at constant temperature for 1.5h, then cooling to about 30 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.5, and obtaining the high-adaptability polycarboxylate superplasticizer with the solid content of 36.5%.
Comparative example 1
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 200.0g of distilled water and 275.0g of monomer B-1, and dissolved by stirring at elevated temperature. The temperature is raised to 85 ℃, then 18.0g of monomer A-1, 1.1g of 3-mercaptopropionic acid and 100.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 3 hours. Simultaneously, initiator solution prepared from 110.0g of distilled water and 5.4g of potassium persulfate is dropwise added at a constant speed for 3.5 h. And after all the solution is dripped, continuously keeping the temperature for 3h at constant temperature, then cooling to about 40 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.0, and obtaining the polycarboxylic acid water reducing agent with the solid content of 41.5%.
Comparative example 2
220.0g of distilled water, 220.0g of monomer B-6 and 0.91g of 30% hydrogen peroxide were put into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at elevated temperature. The temperature is raised to 45 ℃, then 19.5g of monomer A-4, 0.69g of mercaptoethanol, 0.32g L-ascorbic acid and 215.0g of water are mixed and stirred to prepare uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. And after the monomer solution is dropwise added, continuously keeping the temperature at constant temperature for 1.5h, then cooling to about 30 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.5, and obtaining the polycarboxylic acid water reducing agent with the solid content of 35.5%.
Comparative example 3
Into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel were charged 200.0g of distilled water, 275.0g of monomer B-1 and 20.1g of monomer C-1, and dissolved by heating with stirring. The temperature is raised to 85 ℃, then 18.0g of monomer A-1, 1.1g of 3-mercaptopropionic acid and 100.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 3 hours. Simultaneously, initiator solution prepared from 110.0g of distilled water and 5.4g of potassium persulfate is dropwise added at a constant speed for 3.5 h. And after all the solution is dripped, continuously keeping the temperature for 3h at constant temperature, then cooling to about 40 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.0, and obtaining the polycarboxylic acid water reducing agent with the solid content of 43.3%.
Comparative example 4
220.0g of distilled water, 220.0g of monomer B-6, 14.5g of monomer C-3 and 0.91g of 30% hydrogen peroxide were put into a 1L glass round-bottom flask equipped with a thermometer, a stirrer and a dropping funnel, and dissolved by stirring at elevated temperature. The temperature is raised to 45 ℃, then 19.5g of monomer A-4, 0.69g of mercaptoethanol, 0.32g L-ascorbic acid and 225.0g of water are mixed and stirred to prepare a uniform monomer aqueous solution, and the monomer aqueous solution is dropwise added into a round-bottom flask at a constant speed for 2 hours. And after the monomer solution is dropwise added, continuously keeping the temperature at constant temperature for 1.5h, then cooling to about 30 ℃, adding sodium hydroxide for neutralization until the pH value is about 7.5, and obtaining the polycarboxylic acid water reducing agent with the solid content of 36.4%.
The synthesis conditions and the molecular weights of the products of the above-mentioned synthesis examples and comparative examples are shown in Table 2.
TABLE 2 Synthesis conditions and molecular weight of the products in the Synthesis examples and comparative examples
Application example 1
In order to evaluate the clay adaptability of the high-adaptability polycarboxylate water reducer prepared by the invention, the cement net slurry fluidity of the synthetic examples and the comparative examples is tested by referring to the GB/T8077-2012 standard, and the net slurry fluidity is tested after 30 minutes and 1 hour. The test cement is P.II 52.5 cement in small open field in south of the Yangtze river, 300g of cement is weighed, and the water adding amount is 87 g. In the actual test, a small amount of montmorillonite is used for replacing cement with corresponding quality, and the montmorillonite is a 250-mesh powder sample produced in Hebei Tang mountain. The test results are shown in Table 3.
TABLE 3 comparison of neat cement slurries
From the test results: when montmorillonite is not added, compared with the comparative examples, the water reducing performance and the slump retaining performance can be obviously improved after polycation macromolecular chains and phosphate groups are introduced into the polycarboxylic acid structure. After montmorillonite is added, as can be seen from the examples 1, 8 and 12, the synthetic examples can keep the fluidity of the net slurry unchanged only by increasing a little amount of the montmorillonite; as can be seen from comparative example 1, with the increase of the content of montmorillonite, the fluidity can be increased only by greatly increasing the doping amount, the loss is fast, and the fluidity is basically not existed after 60 minutes, which shows that the introduction of polycation macromolecular chains and phosphate groups has obvious advantages on the mud resistance; as can be seen from comparative example 4, with the increase of the content of montmorillonite, the mud resistance of the montmorillonite can be obviously improved after the polycation macromolecular chain is introduced; from the overall examples and comparative examples, it can also be seen that the introduction of phosphate groups has a synergistic effect on the improvement of the water-reducing slump-retaining property and the mud resistance.
Application example 2
To further evaluate the adaptability of the polycarboxylate water reducer prepared by the invention to different regional machine-made sands, the mortar fluidity of the synthetic examples and the comparative examples was tested with reference to the GB/T8077-2012 standard, and the mortar fluidity was tested after 1 hour and 2 hours. The test cement adopts P.II 52.5 cement of small open field in the south of the Yangtze river; the fly ash is south Ning secondary ash; the fine aggregate is prepared from machine-made sand of Guizhou, Sichuan and Zhejiang (the mud content and the stone powder content are different), wherein the content of the machine-made sand of Guizhou is 15%, the MB value is 0.50, the fineness modulus is 2.8, the content of the machine-made sand of Sichuan is 11%, the MB value is 0.75, the fineness modulus is 3.0, the content of the machine-made sand of Zhejiang is 12%, the MB value is 1.35 and the fineness modulus is 2.9. Samples of example 1, example 8, example 12, comparative example 1 and comparative example 4 were selected for the suitability comparison experiment. The mortar mixing proportion is as follows: cement 280, fly ash 70, machine-made sand 750 and water 155. The test results are shown in Table 4.
TABLE 4 mortar comparison results
From the test results, the highly-adaptive polycarboxylate superplasticizers synthesized in the examples 1, 8 and 12 have good adaptability to machine-made sands in different regions, while the comparative example 1 needs to greatly increase the mixing amount to just increase the fluidity and has quick loss, the fluidity is basically not increased after 2 hours, the polycarboxylate superplasticizer synthesized in the comparative example 4 contains polycation macromolecular chains, the small mixing amount is increased, the high-adaptability polycarboxylate superplasticizer has good adaptability to the machine-made sands in different regions, and the introduction of phosphate groups can also greatly improve the water-reducing slump-retaining performance and mud resistance of the polycarboxylate superplasticizer. From the whole examples and comparative examples, the high-adaptability polycarboxylate superplasticizer synthesized by the method has good dispersibility and adaptability to machine-made sand in different regions.
Application example 3
In order to further evaluate the high water-reducing, high slump retaining and mud resistance of the high-adaptability polycarboxylate superplasticizer prepared by the invention, the slump and the expansion degree of concrete are tested by referring to the method specified in GB/T8076-2008 concrete admixture. The cement is P.II 52.5 cement of small wild field in the south of the Yangtze river; the mineral powder is first steel S95 grade mineral powder; the fly ash is south Ning secondary ash; the sand is river sand, the mud content is 3%, and the medium sand with the fineness modulus of 2.6; stones with a particle size of 5-25. Samples of example 1, example 8, example 12, comparative example 1 and comparative example 4 were selected for the suitability comparison experiment. The mixing proportion of the concrete is as follows: 267 cement, mineral powder 53, fly ash 60, sand 767, stone 1060 and water 163. The test results are shown in Table 5.
TABLE 5 comparative data on concrete Properties
From the concrete test results: when the sand and stone material with the mud content of 3% is used for concrete, the synthesized high-adaptability polycarboxylate superplasticizer (examples 1, 8 and 12) can show obvious mud resistance and good water-reducing slump-retaining performance only by low mixing amount; the polycarboxylate superplasticizer without the polycation macromolecular chains (comparative example 1) has initial expansion degree and slump only by greatly increasing the mixing amount, the concrete loss is serious, the expansion degree does not exist after 60 minutes, and the slump is only 95mm, so that the structure of the polycation macromolecular chains can greatly improve the water-reducing slump-retaining performance and the mud resistance; the polycarboxylate superplasticizer synthesized in the comparative example 4 contains polycation macromolecular chains but does not contain phosphate groups, and can also show good water-reducing slump-retaining performance by increasing a little amount of doping, so that the introduction of the phosphate groups can also greatly improve the water-reducing slump-retaining performance and mud resistance of the polycarboxylate superplasticizer, and the polycarboxylate superplasticizer and the polycation macromonomer structure play a synergistic role together.
Claims (10)
1. A high-adaptability polycarboxylate superplasticizer is characterized in that: the molar ratio of 1-5: 1: 0.1-0.3: 0.05-0.2 of carboxylic acid monomer A, high molecular weight polyether macromonomer B, functional macromonomer C and unsaturated phosphate ester monomer D, wherein the free radical copolymerization is carried out to obtain the product, wherein:
the carboxylic acid monomer A has a structure shown in a formula (I):
in the formula，R1Is H or COOM; r2Is H, CH3Or CH2COOM; and when R is1When it is COOM, R2Is not CH at the same time3Or CH2COOM; m is hydrogen atom, alkali metal ion, alkaline earth metal ion, ammonium ion or organic amine group;
the structure of the high molecular weight polyether macromonomer B is shown as the formula (II):
in the formula, R3Is H or CH3；R4H or an alkyl group having 1 to 3 carbon atoms; x1Is CH2、CH2CH2、OCH2CH2Or OCH2CH2CH2CH2(ii) a n is the average addition mole number of polyoxyethylene and is an integer of 25-150;
the functional macromonomer C is maleimide-terminated poly (N-isopropylacrylamide), and the structure of the functional macromonomer C is shown as the formula (III):
wherein m is the average addition mole number of the poly (N-isopropylacrylamide), and is an integer of 5-10;
the unsaturated phosphate ester monomer D has a structure shown in a formula (IV):
in the formula, R5Is H or CH3；R6Is CH2CH2Or CH2CH2CH2。
2. The high-adaptability polycarboxylate water reducer according to claim 1, characterized in that the weight average molecular weight of the high-adaptability polycarboxylate water reducer is 20000-60000.
3. The high-adaptability polycarboxylate water reducer according to claim 2, characterized in that the carboxylic acid monomer A is selected from any one of acrylic acid, methacrylic acid, maleic acid, itaconic acid or sodium salt, potassium salt, calcium salt, ammonium salt and organic amine salt thereof;
the macromolecular polyether macromonomer B is selected from any one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, butenyl polyoxyethylene ether, methyl butenyl polyoxyethylene ether, vinyl polyoxyethylene ether and hydroxybutyl vinyl polyoxyethylene ether;
the functional macromonomer C is selected from maleimide terminated poly (N-isopropylacrylamide);
the unsaturated phosphate ester monomer D is selected from any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
4. The preparation method of the high-adaptability polycarboxylate water reducer as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
(1) dissolving a high molecular weight polyether macromonomer B and a functional macromonomer C in a water solvent, stirring and heating to dissolve into an aqueous solution;
(2) mixing and stirring a carboxylic acid monomer A, an unsaturated phosphoric acid monomer D and water uniformly to obtain a mixed aqueous solution;
(3) dropwise adding the mixed aqueous solution obtained in the step (2) into the solution obtained in the step (1) at a constant speed in the presence of an initiator, continuously keeping the temperature at a constant temperature after all the solutions are dropwise added, carrying out free radical copolymerization on monomers in the solution, and adding an alkaline substance into the solution to neutralize the solution until the pH value is 6-8 after the reaction is finished, so as to obtain the polycarboxylic acid water reducer;
the initiator in the step (3) is a free radical water-soluble initiator and comprises an oxidation initiator and a redox initiator; the oxidation initiator independently selects an oxidation component as an initiator, and the redox initiator selects a composition of the oxidation component and a reduction component as the initiator;
when the initiator is an oxidation initiator, the dosage of the initiator is 0.1 to 2 percent of the total mass of the monomers A, B, C and D; when the initiator is a redox initiator, the total amount of the oxidation components accounts for 0.1-2% of the total mass of the monomers A + B + C + D, and the mass ratio of the oxidation components to the reduction components is 0.4-4: 1;
the mixed aqueous solution in the step (2) also comprises a water-soluble chain transfer agent, and the dosage of the chain transfer agent is 0.05-1% of the total mass of the monomers A + B + C + D;
the oxidizing component in the initiator can be completely fed in one step in the step (1) and mixed with the monomer B and the monomer C, or prepared into an aqueous solution with water and then dripped into the solution in the step (1) with the mixed aqueous solution in the step (2) at a constant speed; and the monomer A, the monomer D, a reducing component in the initiator, a chain transfer agent and water form a mixed aqueous solution, and after the mixed aqueous solution is uniformly stirred, the mixed aqueous solution is added into the solution in the step (1) in a uniform dropping mode.
5. The preparation method of the high-adaptability polycarboxylate water reducer according to claim 4, characterized in that the temperature of the free radical copolymerization reaction in the step (3) is 35-85 ℃, and the dropping time of the mixed aqueous solution is controlled to be 2-5 hours; the dropping time of the initiator oxidizing component solution is prolonged by 0.5 hour compared with the mixed aqueous solution; and continuously preserving the heat after the initiator solution is dripped, wherein the heat preservation time is 1-5 h.
6. The preparation method of the high-adaptability polycarboxylate water reducer according to claim 5, wherein the oxidation initiator comprises persulfate; the redox initiator comprises a composition of persulfate and any one of bisulfite, sulfite, thiosulfate, pyrosulfite or ferrous salt, or a composition of peroxide and any one of sodium formaldehyde sulfoxylate or L-ascorbic acid; the chain transfer agent is a mercaptan chain transfer agent.
7. The preparation method of the high-adaptability polycarboxylate water reducer as claimed in claim 6, wherein the alkaline substance in step (3) comprises a hydroxide, an oxide or a carbonate of a monovalent metal and/or a divalent metal, ammonium hydroxide and an organic amine.
8. The preparation method of the high-adaptability polycarboxylate water reducer according to claim 7, characterized in that the oxidation initiator is selected from potassium persulfate;
the redox initiator may be selected from the group consisting of a combination of hydrogen peroxide and L-ascorbic acid, a combination of potassium persulfate and sodium bisulfite, and a combination of hydrogen peroxide and sodium formaldehyde sulfoxylate;
the chain transfer agent can be selected from 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptopropanol, 3-mercaptopropanol, thioglycolic acid and mercaptoethanol;
the alkaline substance is selected from sodium hydroxide, triethanolamine, potassium hydroxide, and triisopropanolamine.
9. The preparation method of the high-adaptability polycarboxylate water reducer according to claim 8, wherein the mass concentration of the carboxylic acid monomer A, the high-molecular polyether macromonomer B, the functional macromonomer C and the unsaturated phosphoric acid monomer D in the step (3) during polymerization is 35-50%.
10. The application method of the high-adaptability polycarboxylate water reducer as claimed in any one of claims 1 to 3, characterized in that the high-adaptability polycarboxylate water reducer is added in an amount of 0.1-0.5% by weight of the total cementing material.
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| CN112094384B (en) * | 2020-08-10 | 2021-05-14 | 江苏亚琛材料科技有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261719A (en) * | 2014-08-06 | 2015-01-07 | 中交武汉港湾工程设计研究院有限公司 | High-performance polycarboxylate water reducing agent and preparation method thereof |
| CN105017479A (en) * | 2015-06-29 | 2015-11-04 | 合肥工业大学 | Preparation method of anti-clay type polycarboxylate superplasticizer |
| CN105130251A (en) * | 2015-08-28 | 2015-12-09 | 重庆助扬建材有限公司 | Early-strength polycarboxylate water reducing agent and preparing method thereof |
| CN105542091A (en) * | 2015-12-16 | 2016-05-04 | 广东复特新型材料科技有限公司 | Slow-release cationic anti-mud polycarboxylic-type high performance water reducer and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611254169.5A patent/CN107337766B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261719A (en) * | 2014-08-06 | 2015-01-07 | 中交武汉港湾工程设计研究院有限公司 | High-performance polycarboxylate water reducing agent and preparation method thereof |
| CN105017479A (en) * | 2015-06-29 | 2015-11-04 | 合肥工业大学 | Preparation method of anti-clay type polycarboxylate superplasticizer |
| CN105130251A (en) * | 2015-08-28 | 2015-12-09 | 重庆助扬建材有限公司 | Early-strength polycarboxylate water reducing agent and preparing method thereof |
| CN105542091A (en) * | 2015-12-16 | 2016-05-04 | 广东复特新型材料科技有限公司 | Slow-release cationic anti-mud polycarboxylic-type high performance water reducer and preparation method thereof |
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