CN112745057B - Slump retaining additive and preparation method thereof - Google Patents
Slump retaining additive and preparation method thereof Download PDFInfo
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- CN112745057B CN112745057B CN202110044725.0A CN202110044725A CN112745057B CN 112745057 B CN112745057 B CN 112745057B CN 202110044725 A CN202110044725 A CN 202110044725A CN 112745057 B CN112745057 B CN 112745057B
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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Abstract
The application relates to the field of concrete admixtures, and particularly discloses a slump retaining admixture and a preparation method thereof. The slump retaining additive comprises the following components in parts by weight: 100 parts of prenyl alcohol polyoxyethylene ether; 8-15 parts of acrylic acid; 15-22 parts of hydroxyethyl acrylate; 1-2 parts of a reducing agent; 0.1-0.5 part of initiator; 0.5-1 part of chain transfer agent; 4-8 parts of water-soluble sulfate; 1-5 parts of acid soybean seed gum; 0.01-0.8 part of mixture A; 180 portions of water and 250 portions of water; the mixture A consists of superfine titanium dioxide and starch, the particle size of the superfine titanium dioxide is 20-80nm, and the mixture A is obtained by the following steps: adding 60-80 wt% of ethanol aqueous solution while stirring starch, continuing stirring for 10-20min after the addition is finished to obtain treated starch, spraying the treated starch into the superfine titanium dioxide, keeping stirring at 200r/min during the spraying process, and dispersing for 3min under the condition of 800-2000r/min after the addition of the treated starch is finished to obtain a mixture A. Has the advantage of reducing the slump loss of the concrete in the middle and later periods.
Description
Technical Field
The application relates to the field of concrete admixtures, in particular to a slump retaining admixture and a preparation method thereof.
Background
With the development of commercial concrete industry for construction, concrete admixtures have been widely used. The concrete admixture is a chemical substance which is added in the process of stirring the concrete, accounts for less than 5 percent of the mass of the cement and can obviously improve the performance of the concrete.
Along with the popularization and application of premixed concrete, the long-distance transportation of the concrete gradually reduces the construction performance of the concrete, the quality of the concrete cannot be well guaranteed in the construction process, and the problem of large slump loss of the concrete is particularly serious. The slump loss preventing additive can provide a good slump loss preventing effect for concrete, and the slump loss of the concrete is greatly reduced.
In the related art, esters such as maleic anhydride monomethyl esters and acrylic acid hydroxy ethyl esters are frequently used in the slump retaining admixture, and due to the introduction of ester groups, the ester groups can slowly release carboxyl along with the alkaline environment provided by cement hydration, and the carboxyl is adsorbed outside cement molecules, so that the effect of slowly releasing slump retaining is realized. However, the initial adsorption capacity of the slump retaining additive outside cement particles is low, and the early slump loss is large. In order to solve the above problems, the anions can be added to be adsorbed outside the cement particles at the initial time point, but the anions and the carboxyl groups are adsorbed outside the cement particles to compete, which is not favorable for stabilizing the slump retaining effect at the middle and later stages.
Disclosure of Invention
In order to reduce slump loss of concrete in the middle and later stages, the application provides a slump-retaining additive and a preparation method thereof.
In a first aspect, the present application provides the following technical solutions: the slump loss resistant additive is characterized by comprising the following components in parts by weight:
100 parts of prenyl alcohol polyoxyethylene ether;
8-15 parts of acrylic acid;
15-22 parts of hydroxyethyl acrylate;
1-2 parts of a reducing agent;
0.1-0.5 part of initiator;
0.5-1 part of chain transfer agent;
4-8 parts of water-soluble sulfate;
1-5 parts of acid soybean seed gum;
0.01-0.8 part of mixture A;
180 portions of water and 250 portions of water;
the mixture A consists of superfine titanium dioxide and starch and is obtained by the following steps:
adding 60-80 wt% of ethanol aqueous solution while stirring starch, continuing stirring for 10-20min after the addition is finished to obtain treated starch, spraying the treated starch into the superfine titanium dioxide, keeping stirring at 200r/min during the spraying process, and dispersing for 3min under the condition of 800-2000r/min after the addition of the treated starch is finished to obtain a mixture A.
By adopting the technical scheme, the prenol polyoxyethylene ether, the acrylic acid and the hydroxyethyl acrylate are used as monomers, and the prenol polyoxyethylene ether, the acrylic acid and the hydroxyethyl acrylate are reacted with the initiator, the reducing agent and the chain transfer agent to synthesize the hydroxyethyl acrylate. The hydroxyethyl acrylate carries an ester group, in the cement hydration process, an alkaline environment is provided for the hydroxyethyl acrylate, the ester group is gradually hydrolyzed into hydroxyl in the alkaline environment, the hydroxyl belongs to a polar group and can be adsorbed on the surfaces of cement particles or hydration products, the interaction force among the cement particles is changed through steric hindrance, a hydration film is formed on the surfaces of the cement particles, the hydration of the cement particles and the coagulation or precipitation among the particles are inhibited, the fluidity of cement paste is maintained, and the slump retaining effect is realized.
The water-soluble sulfate can hydrolyze to obtain sulfate anions in water, and sulfate can be adsorbed on the surface of cement particles to play a role in slowing down the hydration of cement. Sulfate radicals can be adsorbed on the surfaces of cement particles at the initial time point, the early hydration reaction is slowed down, and the slump retaining effect at the initial stage is ensured by matching with hydroxyethyl acrylate. However, with the lapse of time, anions initially adsorbed to the outside of cement particles compete with hydroxyl groups generated by hydrolysis to adsorb, and the slump retaining effect in the middle and later stages is affected.
Acid soybean seed gum and mixture A were also added. The sour soybean seed gum has emulsifying effect and water-holding effect. In the mixture A, the superfine titanium dioxide basically has no covering power and is transparent due to small particle size, and has good stability. Starch is composed of glucose units as the main component and has a helical structure. In the preparation method of the mixture A, the starch treated by the 60-80 wt% ethanol water solution has smaller fineness and higher dryness, and has better adsorption and coating effects on the surface of the superfine titanium dioxide.
Tests show that after the ultrafine titanium dioxide is treated with the starch, the starch can be well adsorbed on the surface of the ultrafine titanium dioxide; and the slump loss of the medium and later stages can be well reduced by matching with the acid soybean seed gum, and the slump loss prevention effect is improved.
Further, the mass part ratio of the superfine titanium dioxide to the starch in the mixture A is 1: (0.05-0.1).
By adopting the technical scheme, experiments show that the mixture A with better adsorption and coating effects is obtained by matching with the preparation method, and has better positioning and coating effects in the formula.
Further, the mass part ratio of the acid soybean seed gum to the superfine titanium dioxide is (2-5): 1.
by adopting the technical scheme, tests show that better slump retaining effect in the middle and later periods can be obtained.
Further, the mixture a is obtained by the following steps: adding 60-80 wt% of ethanol aqueous solution while stirring starch, continuing stirring for 10-20min after the addition is finished to obtain treated starch, spraying the treated starch into the superfine titanium dioxide, keeping stirring at 200r/min during the spraying process, dispersing for 1-3min under the condition of 800-2000r/min after the addition of the treated starch is finished, heating to 50-80 ℃, cooling to 20 +/-5 ℃, and completing the heating and cooling within 3-5min to obtain a mixture A.
Through adopting above-mentioned technical scheme, mix the back of accomplishing, through the intensification in the short time and the cooling, can be known by the experiment, the slump loss prevention effect in the assurance middle and later stages that can be better.
Further, the sour soybean seed gum comprises dehydroxanthan gum, wherein the mass part ratio of the sour soybean seed gum to the dehydroxanthan gum is 1: (0.12-0.25).
By adopting the technical scheme, the dehydrogenated xanthan gum has the film forming effect and the weak water catching effect. Tests show that better slump retaining effect can be obtained.
Further, 0.3-1.5 parts of behenyl trimethyl ammonium methyl sulfate is also included.
By adopting the technical scheme, the behenyl trimethyl ammonium methyl sulfate has the function of a surfactant. Tests show that the slump retaining effect in the middle and later stages can be improved.
Further, the mass part ratio of the acid bean seed gum to the behenyl trimethyl ammonium methyl sulfate is 1: (0.3-0.35).
By adopting the technical scheme, the test shows that the slump retaining effect in the middle and later stages can be further improved.
In a second aspect, the present application provides the following technical solutions: a preparation method of the slump retaining additive comprises the following steps: s1: mixing acrylic acid, hydroxyethyl acrylate, water accounting for 90 percent of the total amount and isoamylol polyoxyethylene ether, heating to 80-90 ℃, preserving heat, adding a reducing agent, an initiator and a chain transfer agent, reacting at 50-60 ℃ for 3-4h, stopping heating, and cooling to obtain a first component;
s2: adding the acid soybean seed gum, the dehydrogen reduction gum, the behenyl trimethyl ammonium methyl sulfate and the rest water into the mixture A, and uniformly mixing to obtain a second component;
s3: uniformly mixing the first component and the second component at the temperature of 25-40 ℃ to obtain a slump retaining additive;
the steps S1 and S2 may be performed simultaneously.
By adopting the technical scheme, the hydroxyethyl acrylate is synthesized by S1, and other components which are uniformly mixed are added to obtain the uniform and stable slump retaining additive.
In summary, the present application has the following beneficial effects:
1. the compound of the mixture A and the acid soybean seed gum is preferably adopted in the application, so that the slump loss degree in the middle and later stages can be well reduced, and the slump retaining effect is improved.
2. In the application, the mixture A is prepared by preferably compounding the starch treated by the ethanol with the superfine titanium dioxide, the fineness is smaller, the dryness is higher, the adsorption and coating effects on the surface of the superfine titanium dioxide are better, and the slump retaining effect is further improved.
3. In the application, ethanol is preferably adopted to treat starch, and high-temperature and low-temperature treatment is carried out to obtain a mixture A, so that the slump retaining effect is further improved.
4. The application preferably adopts dehydrogenated xanthan gum, and can further obtain better slump retaining effect.
Detailed Description
Examples
Example 1: a slump retaining additive comprises the components and the corresponding mass shown in a table 1.1, and is prepared by the following steps:
s1: adding acrylic acid, hydroxyethyl acrylate, water accounting for 90% of the total amount and isoamylol polyoxyethylene ether into a reactor provided with a thermometer, an electric stirring ball and a condensation reflux tank, heating to 80 ℃ under the protection of nitrogen, preserving heat, sequentially adding a reducing agent, an initiator and a chain transfer agent, cooling to 50 ℃, stopping heating after reacting for 3 hours, and naturally cooling to obtain a first component;
s2: putting the mixture A into a stirrer, sequentially adding the acid soybean seed gum, the dehydrogen reduction gum (in the embodiment, the component is added), the behenyl trimethyl ammonium methyl sulfate (in the embodiment, the component is added) and the rest of water at the temperature of 25 +/-5 ℃ and the stirring speed of 200r/min, and stirring for 10min to obtain a second component;
s3: and adding the first component into the second component, and uniformly mixing at the temperature of 25 ℃ to obtain the slump retaining additive.
Steps S1 and S2 may be performed simultaneously.
Preparation of mixture a: and (2) putting the starch into an open mixer A, starting stirring at the speed of 150/min, adding an ethanol aqueous solution with the mass of 60% by weight at the temperature of 25 +/-5 ℃, and continuing stirring for 10min after the addition is finished to obtain the treated starch. And (3) putting the superfine titanium dioxide into a mixer B, starting the stirring speed to be 100r/min, spraying the treated starch into the superfine titanium dioxide by a powder spraying machine within 10min, and dispersing for 3min under the condition of 800r/min after the treated starch is added to obtain a mixture A.
Example 2: a slump-retaining admixture differing from example 1 in that preparation of mixture A: and (2) putting the starch into an open mixer A, starting stirring at the speed of 200/min, adding 80 wt% of ethanol aqueous solution at the temperature of 25 +/-5 ℃, and continuing stirring for 8min after the addition is finished to obtain the treated starch. And (3) putting the superfine titanium dioxide into the mixer B, starting the stirring speed to be 200r/min, spraying the treated starch into the superfine titanium dioxide by a powder sprayer, and finishing spraying within 7min to obtain a mixture A.
Example 3: a slump-retaining admixture differing from example 1 in that preparation of mixture A: after spraying the superfine titanium dioxide in the superfine titanium dioxide, heating the mixer B to 50 ℃, cooling to 20 +/-5 ℃, completing heating and cooling within 3min, and cooling in a manner of blowing cold air to the shell of the mixer B to obtain a mixture A.
Example 4: a slump-retaining admixture differing from example 1 in that preparation of mixture A: after spraying the superfine titanium dioxide in the superfine titanium dioxide, heating the mixer B to 80 ℃, cooling to 20 +/-5 ℃, completing heating and cooling within 5min, and cooling by blowing cold air to the shell of the mixer B to obtain a mixture A.
Examples 5 to 8: a slump-retaining admixture differing from example 3 in the components included and the corresponding masses are shown in Table 1.1.
Examples 9 to 16: a slump-retaining admixture differing from example 3 in the components included and the corresponding masses are shown in Table 1.2.
TABLE 1.1 examples 1, 5-8 components and corresponding masses (kg)
TABLE 1.2 examples 9-16 compositions and corresponding masses (kg)
In the embodiment, the reducing agent is 30 wt% of hydrogen peroxide; the initiator is azodicyano valeric acid; the chain transfer agent is sodium methyl propylene sulfonate; the water-soluble sulfate is magnesium sulfate. The ultrafine silica was purchased from Hangzhou Hengge nanotechnology Co., Ltd, and had an average primary particle size of 30 nm.
Example 17: a preparation method of the slump retaining additive comprises the following steps: s1: adding acrylic acid, hydroxyethyl acrylate, water accounting for 90% of the total amount and isoamylol polyoxyethylene ether into a reactor provided with a thermometer, an electric stirring ball and a condensation reflux tank, heating to 90 ℃ under the protection of nitrogen, preserving heat, sequentially adding a reducing agent, an initiator and a chain transfer agent, cooling to 60 ℃, stopping heating after reacting for 4 hours, and naturally cooling to obtain a first component;
s2: putting the mixture A into a stirrer, sequentially adding the acid soybean seed gum, the dehydrogen reduction gum (in the embodiment, the component is added), the behenyl trimethyl ammonium methyl sulfate (in the embodiment, the component is added) and the rest of water at the temperature of 25 +/-5 ℃ and the stirring speed of 100r/min, and stirring for 15min to obtain a second component;
s3: and adding the first component into the second component, and uniformly mixing at the temperature of 25 ℃ to obtain the slump retaining additive.
Steps S1 and S2 may be performed simultaneously.
Preparation of mixture a: as in example 1.
Comparative example
Comparative example 1: the difference from example 1 is that mixture A and acid soybean seed gum are replaced with an equal amount of water.
Comparative example 2: the difference from example 1 is that mixture A is replaced by an equal amount of water.
Comparative example 3: the difference from example 1 is that the acid soybean seed gum was replaced with an equal amount of water.
Comparative example 4: the difference from example 1 is that mixture A is titanium dioxide with a particle size of 50 μm.
Comparative example 5: the difference from example 1 is that the tapioca starch in mixture a is replaced by an equal amount of water.
Characterization test:
1. slump loss test
Test subjects: examples 1-16 and comparative examples 1-5, for a total of 21 test samples.
The test method comprises the following steps: examples 1 to 16 and comparative examples 1 to 5 were mixed uniformly with concrete at a content of 0.05%, and slump loss was examined. The concrete formula comprises: 150kg of cement, 75kg of mineral powder, 70kg of fly ash, 820 parts of medium sand and 500kg of stones, and can be prepared in large quantities according to the mixture ratio. Each concrete portion was 500kg, and 0.05% of the test specimen was incorporated and mixed uniformly to obtain examples 1 to 16 and comparative examples 1 to 5, and a blank set without adding the slump-retaining additive.
Slump test method: filling concrete into a horn-shaped slump bucket with an upper opening of 100mm, a lower opening of 200mm and a height of 300mm, filling the concrete for three times, uniformly impacting 25 times along the wall of the bucket from outside to inside by using a tamping hammer after each filling, tamping and leveling. And then the barrel is pulled up, the concrete generates a collapse phenomenon due to self weight, and the height of the highest point of the collapsed concrete is subtracted by the height of the barrel, namely the collapse degree. If the difference is 100mm, the slump is 100.
Slump tests are carried out at 0min, 20min, 60min and 90min after the concrete is prepared, and slump loss (%) relative to 0min at 20min, 60min and 90min is calculated as (0min slump-20/60/90 min slump)/0 min slump.
And (3) test results: slump loss test results are reported in table 2.
TABLE 2 slump loss test results record
And (3) data analysis: as can be seen from the data in Table 2, the examples had better slump loss at the middle and later stages than the comparative examples, wherein the slump loss at the later stage was smaller.
The data show that the middle and late slump loss is less for the samples prepared from the combination of acid soybean seed gum and mixture a, which is prepared from ultrafine titanium dioxide and starch, compared to the comparative examples. The possible reasons are: during the middle and later period, the water-catching effect of the acid soybean seed gum can reduce the dissociation of water molecules, and the superfine titanium dioxide which adsorbs the starch is used as a physical positioning point. On one hand, the sour soybean seed gum is matched with starch on the outer surface of the superfine titanium dioxide to perform point location on the hydroxyethyl acrylate, so that the dissociation of the hydroxyethyl acrylate is reduced, and on the other hand, the loosening and the separation of sulfate radicals on the surfaces of cement particles in the middle and later periods can be promoted. And further forms coating and isolation outside the obtained hydration product, and slows down the progress of hydration and coagulation of the hydration product. The application of sulfate radicals and hydroxyethyl acrylate ensures the early slump retaining effect, and then the absorption capacity of the sulfate radicals and hydroxyl radicals at the middle and later stages outside cement particles and hydration products is balanced by the mixture A and the acid soybean seed gum, and the slump retaining effect at the whole stage is comprehensively ensured by further coating and isolating.
Comparative example 1 was run with the mixture a and acid pea seed gum removed, comparative example 2 was run with the mixture a removed, comparative example 3 was run with the acid pea seed gum removed, comparative example 4 was run with 50 μm titanium dioxide instead of mixture a, and comparative example 5 was run with the mixture a tapioca removed. Compared with the example 1, the slump retaining effect in the middle and later stages can be well improved by compounding the acid soybean seed gum and the mixture A.
In the examples, examples 3 to 6 improved the preparation method of the mixture a compared with examples 1 to 2, and a better slump retaining effect was obtained in the middle and later stages, probably because: the preparation method improves the adhesion of the starch outside the superfine titanium dioxide, improves the integrity of the mixture A, and has better positioning and coating effects on cement particles.
Examples 7 to 8 define the dosage ratio of the ultrafine titanium dioxide and the starch in the mixture A on the basis of example 5, and examples 9 to 10 define the dosage ratio of the acid soybean seed gum and the mixture A on the basis of example 8, so that the adsorption amounts of sulfate radicals and carboxyl groups are better balanced, and the slump retaining effect in the middle and later stages is further improved.
Examples 11 to 12 additionally use dehydroxanthan gum on the basis of example 10, which improves the film forming effect of the acid soybean seed gum outside the cement particles, improves the coating effect on the cement particles, and obtains better slump retaining effect in the middle and later stages. Examples 13-16 are based on example 11 and additionally use behenyl trimethyl ammonium methyl sulfate, and further improve the slump retaining effect in the middle and later periods. The reasons may be: the carboxyl on part of single chain segment can connect cement particles and new adsorption vacancy, thereby improving the carboxyl adsorption quantity on the surface of the cement particles and the ester adsorption quantity. Meanwhile, the ester group adsorption can be fixed by film formation, and the slump retaining effect is improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (7)
1. The slump loss resistant additive is characterized by comprising the following components in parts by weight:
100 parts of prenyl alcohol polyoxyethylene ether;
8-15 parts of acrylic acid;
15-22 parts of hydroxyethyl acrylate;
1-2 parts of a reducing agent;
0.1-0.5 part of initiator;
0.5-1 part of chain transfer agent;
4-8 parts of water-soluble sulfate;
1-5 parts of acid soybean seed gum;
0.01-0.8 part of mixture A;
180 portions of water and 250 portions of water;
the mixture A consists of superfine titanium dioxide and starch, the particle size of the superfine titanium dioxide is 20-80nm, and the mixture A is obtained by the following steps:
adding 60-80 wt% of ethanol aqueous solution while stirring starch, continuing stirring for 10-20min after the addition is finished to obtain treated starch, spraying the treated starch into the superfine titanium dioxide, keeping stirring at 200r/min during the spraying process, and dispersing for 3min under the condition of 800-2000r/min after the addition of the treated starch is finished to obtain a mixture A.
2. The slump retaining additive as claimed in claim 1, wherein the mass part ratio of the ultrafine titanium dioxide to the starch in the mixture A is 1: (0.05-0.1).
3. The slump retaining additive as claimed in claim 2, wherein the weight ratio of the acid soybean seed gum to the superfine titanium dioxide is (2-5): 1.
4. the slump retaining additive as claimed in claim 1, wherein the mixture A is obtained by the following steps: adding 60-80 wt% of ethanol aqueous solution while stirring starch, continuing stirring for 10-20min after the addition is finished to obtain treated starch, spraying the treated starch into the superfine titanium dioxide, keeping stirring at 200r/min during the spraying process, dispersing for 1-3min under the condition of 800-2000r/min after the addition of the treated starch is finished, heating to 50-80 ℃, cooling to 20 +/-5 ℃, and completing the heating and cooling within 3-5min to obtain a mixture A.
5. The slump-retaining additive as claimed in claim 1, further comprising dehydroxanthan gum, wherein the weight part ratio of the acid soybean seed gum to the dehydroxanthan gum is 1: (0.12-0.25).
6. The slump retaining additive as claimed in claim 1, further comprising 0.3-1.5 parts of behenyl trimethyl ammonium methyl sulfate.
7. The slump retaining additive as claimed in claim 6, wherein the mass part ratio of the acid soybean gum to the behenyl trimethyl ammonium methyl sulfate is 1: (0.3-0.35).
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| US6187841B1 (en) * | 1995-07-13 | 2001-02-13 | Mbt Holding Ag | Cement composition using the dispersant of (meth)acrylic esters, (metha)acrylic acids polymers |
| CN105367720A (en) * | 2015-11-25 | 2016-03-02 | 科之杰新材料集团有限公司 | Water-reducing slump-retaining type polycarboxylic acid water reducing agent and preparing method thereof |
| CN108285286A (en) * | 2018-02-28 | 2018-07-17 | 湖北工业大学 | A kind of preparation method of polycarboxylate water-reducer suitable for mortar |
| CN110358011A (en) * | 2018-04-10 | 2019-10-22 | 北京砼帮汇科技有限公司 | A kind of cement water reducing agent |
| CN111548459A (en) * | 2020-05-15 | 2020-08-18 | 厦门路桥翔通建材科技有限公司 | Preparation method of high slump loss resistant polycarboxylate superplasticizer |
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2021
- 2021-01-13 CN CN202110044725.0A patent/CN112745057B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6187841B1 (en) * | 1995-07-13 | 2001-02-13 | Mbt Holding Ag | Cement composition using the dispersant of (meth)acrylic esters, (metha)acrylic acids polymers |
| CN105367720A (en) * | 2015-11-25 | 2016-03-02 | 科之杰新材料集团有限公司 | Water-reducing slump-retaining type polycarboxylic acid water reducing agent and preparing method thereof |
| CN108285286A (en) * | 2018-02-28 | 2018-07-17 | 湖北工业大学 | A kind of preparation method of polycarboxylate water-reducer suitable for mortar |
| CN110358011A (en) * | 2018-04-10 | 2019-10-22 | 北京砼帮汇科技有限公司 | A kind of cement water reducing agent |
| CN111548459A (en) * | 2020-05-15 | 2020-08-18 | 厦门路桥翔通建材科技有限公司 | Preparation method of high slump loss resistant polycarboxylate superplasticizer |
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