CN109020292B - Preparation method of environment-friendly enhanced alkali-free liquid accelerator - Google Patents
Preparation method of environment-friendly enhanced alkali-free liquid accelerator Download PDFInfo
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- CN109020292B CN109020292B CN201810937456.9A CN201810937456A CN109020292B CN 109020292 B CN109020292 B CN 109020292B CN 201810937456 A CN201810937456 A CN 201810937456A CN 109020292 B CN109020292 B CN 109020292B
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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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
Abstract
The invention discloses a preparation method of an environment-friendly enhanced alkali-free liquid accelerator. The preparation method of the invention prepares acylation products by acylating maleic anhydride and urea, and then copolymerizes the acylation products with acrylamide and acrylic acid to prepare the suspension stabilizer which is used for synthesizing the alkali-free liquid accelerator. The suspension stabilizer with the amide structure is prepared by introducing maleic anhydride and urea for acylation, so that the coagulability of the liquid accelerator is improved, the generation of precipitates is effectively inhibited, the storage stability of the mother liquor is greatly improved, and the stability can reach more than 15 months; and the amide structure and the urea can promote the development of early strength, thereby improving the early strength of the concrete.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a preparation method of an environment-friendly enhanced alkali-free liquid accelerator.
Background
Along with the acceleration of large-scale mining, tunnel excavation and road network and railway network engineering construction, the use amount of the accelerator is greatly increased, and higher requirements are provided for the performance and quality of the accelerator. The traditional powdery accelerator product can only be applied to dry spraying process construction and has the defects of low dissolving speed, difficult uniform dispersion and the like.
At present, the development trend of the accelerator for shotcrete is changing from the traditional solid powder to liquid, and the low-alkali-free accelerator gradually replaces the traditional accelerator. The liquid accelerator adopted at present in China has the problems of high alkali content, large later strength loss, poor impermeability of hardened concrete and the like. The alkali content is high, the environmental pollution is serious, the harm to constructors is large, the concrete quality is unstable, and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly enhanced alkali-free liquid accelerator.
The technical scheme of the invention is as follows:
a preparation method of an environment-friendly enhanced alkali-free liquid accelerator comprises the following steps:
(1) acylation reaction: adding maleic anhydride and urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding a catalyst, slowly heating to 70-90 ℃, keeping the temperature for 1.5-4 hours, and cooling to obtain an acylation product, wherein the molar ratio of the maleic anhydride to the urea is 1: 1-2;
(2) preparation of suspension stabilizer: dripping the acylation product, acrylamide aqueous solution, acrylic acid aqueous solution, ammonium persulfate aqueous solution and molecular weight regulator aqueous solution into water for reaction, wherein the reaction temperature is 50-90 ℃, the dripping time is 1.0-4.0 h, and the heat preservation time is 0-3.0 h to obtain a suspension stabilizer; the total amount of water used in the step enables the mass concentration of the suspension stabilizer to be 5-40%, and the mass ratio of the acylation product, the acrylamide solution and the acrylic acid solution is 1: 1-2: 0.2-1;
(3) preparation of the reinforcing agent: reacting alcohol amine and oxalic acid at the reaction temperature of 50-90 ℃, adding a catalyst, and reacting for 1-4 hours to obtain a first mixture; adding glycerol into the first mixture to react at the temperature of 70-90 ℃ for 1-4h to obtain a reinforcing agent; the mol ratio of the alcohol amine to the oxalic acid to the glycerol is 1: 0.4-1.2; the alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, diethanol monoisopropanolamine and monoethanol diisopropanolamine;
the catalyst in the step (1) and the step (3) is p-toluenesulfonic acid and/or concentrated sulfuric acid;
(4) adding 0.2-3.0 parts by weight of the suspension stabilizer prepared in the step (2) and 1-10 parts by weight of the pH value regulator into water, stirring, reacting at 10-60 ℃, adding 30-60 parts by weight of aluminum sulfate, adding 1-20 parts by weight of the reinforcing agent prepared in the step (3) after 0.2-2.0 hours, and reacting for 0.2-1 hour to obtain the environment-friendly enhanced alkali-free liquid accelerator; the total amount of water used in the step enables the mass concentration of the environment-friendly enhanced alkali-free liquid accelerator to be 40-70%.
In a preferred embodiment of the present invention, in the step (1), the catalyst is used in an amount of 0.3 to 0.6% by mass based on the total mass of maleic anhydride and urea.
In a preferred embodiment of the present invention, in the step (2), the amount of the ammonium persulfate is 0.5 to 3.0% of the total mass of the solute in the acylation product, the acrylamide solution and the acrylic acid solution,
in a preferred embodiment of the present invention, in the step (2), the molecular weight modifier is used in an amount of 0.2 to 3.0% based on the total mass of the solutes in the acylate, the acrylamide solution and the acrylic acid solution.
In a preferred embodiment of the present invention, in the step (3), the amount of the catalyst is 0.3 to 4.0% of the total mass of the alcohol amine and the oxalic acid.
Further preferably, the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, and dodecanethiol.
Further preferably, the pH adjuster is at least one of concentrated sulfuric acid, p-toluenesulfonic acid, citric acid, tartaric acid, salicylic acid, and hydrofluoric acid.
The invention has the beneficial effects that:
1. the preparation method of the invention prepares acylation products by acylating maleic anhydride and urea, and then copolymerizes the acylation products with acrylamide and acrylic acid to prepare the suspension stabilizer which is used for synthesizing the alkali-free liquid accelerator. The suspension stabilizer with the amide structure is prepared by introducing maleic anhydride and urea for acylation, so that the coagulability of the liquid accelerator is improved, the generation of precipitates is effectively inhibited, the storage stability of the mother liquor is greatly improved, and the stability can reach more than 15 months; and the amide structure and the urea can promote the development of early strength, thereby improving the early strength of the concrete.
2. According to the preparation method, the reinforcing agent is prepared by esterifying the alcohol amine with the ethanedioic acid and then esterifying the alcohol amine with the glycerol, and the reinforcing agent is applied to synthesis of the alkali-free liquid accelerator, so that the early strength and the later strength of the concrete can be improved.
3. The environment-friendly enhanced alkali-free liquid accelerator prepared by the invention has no corrosivity on the skin of construction workers, has no pollution to the production environment, and belongs to a green pollution-free product.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
(1) Acylation reaction: adding 100.00g of maleic anhydride and 65.00g of urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding 0.50g of p-toluenesulfonic acid, slowly heating to 75 ℃, keeping the temperature for 2.0 hours, and cooling to obtain an acylated product;
(2) preparation of suspension stabilizer: dropping 100.00g of acylation product, an acrylamide aqueous solution (wherein 130.00g of acrylic acid and 150.00g of water), an acrylic acid aqueous solution (wherein 30.00g of acrylic acid and 150.00g of water), an ammonium persulfate aqueous solution (wherein 2.20g of ammonium persulfate and 150.00g of water) and a thioglycolic acid aqueous solution (wherein 1.60g of thioglycolic acid and 150.00g of water) into 500.00g of water for reaction at the reaction temperature of 70 ℃ for 2.0h, and preserving the heat for 1.0h to obtain a suspension stabilizer;
(3) preparation of the reinforcing agent: reacting 105.00g of diethanolamine with 90.00g of oxalic acid at the reaction temperature of 60 ℃, and then adding 1.00g of p-toluenesulfonic acid for 2 hours to obtain a first mixture; adding 46.00g of glycerol into the first mixture to react at the temperature of 70 ℃ for 3.0h to obtain a reinforcing agent;
(4) and (3) adding 1.00g of the suspension stabilizer prepared in the step (2) and 3.00g of concentrated sulfuric acid into 50.00g of water, stirring, reacting at the temperature of 40 ℃, adding 40.00g of aluminum sulfate, adding 10.00g of the reinforcing agent prepared in the step (3) after 1.0h, and reacting for 0.5h to obtain the environment-friendly enhanced alkali-free liquid accelerator.
Example 2
(1) Acylation reaction: adding 100.00g of maleic anhydride and 70.00g of urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding 0.70g of concentrated sulfuric acid, slowly heating to 75 ℃, keeping the temperature for 3.0 hours, and cooling to obtain an acylation product;
(2) preparation of suspension stabilizer: dropping 100.00g of acylation product, an acrylamide aqueous solution (wherein 140.00g of acrylic acid and 150.00g of water), an acrylic acid aqueous solution (wherein 35.00g of acrylic acid and 150.00g of water), an ammonium persulfate aqueous solution (wherein 1.70g of ammonium persulfate and 150.00g of water) and a mercaptopropionic acid aqueous solution (wherein 1.70g of mercaptopropionic acid and 150.00g of water) into 500.00g of water for reaction at the reaction temperature of 70 ℃ for 3.0h, and preserving the heat for 2.0h to obtain a suspension stabilizer;
(3) preparation of the reinforcing agent: reacting 61.00g of monoethanolamine with 90.00g of oxalic acid at the reaction temperature of 70 ℃, and then adding 0.80g of concentrated sulfuric acid for 3.0h to obtain a first mixture; adding 55.00g of glycerol into the first mixture to react at the temperature of 80 ℃ for 2.0h to obtain a reinforcing agent;
(4) and (3) adding 2.00g of the suspension stabilizer prepared in the step (2) and 5.00g of p-toluenesulfonic acid into 50.00g of water, stirring, reacting at 50 ℃, adding 50.00g of aluminum sulfate, adding 12.00g of the reinforcing agent prepared in the step (3) after 1.5h, and reacting for 0.5h to obtain the environment-friendly enhanced alkali-free liquid accelerator.
Example 3
(1) Acylation reaction: adding 100.00g of maleic anhydride and 66.00g of urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding 0.60g of concentrated sulfuric acid, slowly heating to 80 ℃, keeping the temperature for 2.5 hours, and cooling to obtain an acylated product;
(2) preparation of suspension stabilizer: dropping 100.00g of acylation product, an acrylamide aqueous solution (wherein 150.00g of acrylic acid and 150.00g of water), an acrylic acid aqueous solution (wherein 40.00g of acrylic acid and 150.00g of water), an ammonium persulfate aqueous solution (wherein 2.80g of ammonium persulfate and 150.00g of water) and a mercaptoethanol aqueous solution (wherein 3.00g of mercaptoethanol and 150.00g of water) into 520.00g of water for reaction at the reaction temperature of 80 ℃ for 2.0h, and preserving heat for 3.0h to obtain a suspension stabilizer;
(3) preparation of the reinforcing agent: 149.00g of triethanolamine reacts with 90.00g of oxalic acid at the reaction temperature of 60 ℃, and 1.20g of concentrated sulfuric acid is added for reaction for 1.5h to obtain a first mixture; adding 74.00g of glycerol into the first mixture to react at the temperature of 75 ℃ for 2.0h to obtain a reinforcing agent;
(4) and (3) adding 1.50g of the suspension stabilizer prepared in the step (2) and 4.00g of p-toluenesulfonic acid into 50.00g of water, stirring, reacting at 45 ℃, adding 35.00g of aluminum sulfate, adding 8.00g of the reinforcing agent prepared in the step (3) after 1.0h, and reacting for 0.5h to obtain the environment-friendly enhanced alkali-free liquid accelerator.
Example 4
(1) Acylation reaction: adding 100.00g of maleic anhydride and 80.00g of urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding 0.80g of p-toluenesulfonic acid, slowly heating to 80 ℃, keeping the temperature for 1.5h, and cooling to obtain an acylated product;
(2) preparation of suspension stabilizer: dropping 100.00g of acylation product, an acrylamide aqueous solution (wherein 138.00g of acrylic acid and 150.00g of water), an acrylic acid aqueous solution (wherein 50.00g of acrylic acid and 150.00g of water), an ammonium persulfate aqueous solution (wherein 2.00g of ammonium persulfate and 150.00g of water) and an isopropanol aqueous solution (wherein 2.60g of isopropanol and 150.00g of water) into 520.00g of water for reaction at the reaction temperature of 60 ℃ for 4.0h, and preserving the heat for 2.0h to obtain a suspension stabilizer;
(3) preparation of the reinforcing agent: 191.00g of triisopropanolamine and 90.00g of oxalic acid are reacted at the reaction temperature of 75 ℃, and 1.40g of concentrated sulfuric acid is added for 2.5 hours to obtain a first mixture; adding 65.00g of glycerol into the first mixture to react at 85 ℃ for 1.0h to obtain a reinforcing agent;
(4) and (3) adding 2.00g of the suspension stabilizer prepared in the step (2) and 2.00g of citric acid into 50.00g of water, stirring, reacting at the temperature of 30 ℃, adding 50.00g of aluminum sulfate, adding 13.00g of the reinforcing agent prepared in the step (3) after 0.5h, and reacting for 0.5h to obtain the environment-friendly enhanced alkali-free liquid accelerator.
Example 5
(1) Acylation reaction: adding 100.00g of maleic anhydride and 100.00g of urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding 1.00g of concentrated sulfuric acid, slowly heating to 85 ℃, keeping the temperature for 3.5 hours, and cooling to obtain an acylation product;
(2) preparation of suspension stabilizer: dropping 100.00g of acylation product, an acrylamide aqueous solution (wherein 160.00g of acrylic acid and 150.00g of water), an acrylic acid aqueous solution (wherein 60.00g of acrylic acid and 150.00g of water), an ammonium persulfate aqueous solution (wherein 2.60g of ammonium persulfate and 150.00g of water) and a thioglycolic acid aqueous solution (wherein 2.50g of thioglycolic acid and 150.00g of water) into 600.00g of water for reaction at the reaction temperature of 65 ℃ for 3.0h, and preserving heat for 1.0h to obtain a suspension stabilizer;
(3) preparation of the reinforcing agent: 163.20g of diethanol monoisopropanolamine and 90.00g of oxalic acid are reacted at the reaction temperature of 80 ℃, 1.30g of concentrated sulfuric acid is added, and the reaction time is 3.0h, so that a first mixture is obtained; adding 90.00g of glycerol into the first mixture to react at the temperature of 80 ℃ for 2.0h to obtain a reinforcing agent;
(4) and (3) adding 1.00g of the suspension stabilizer prepared in the step (2) and 6.00g of tartaric acid into 50.00g of water, stirring, reacting at the temperature of 20 ℃, adding 45.00g of aluminum sulfate, adding 15.00g of the reinforcing agent prepared in the step (3) after 1.0h, and reacting for 0.5h to obtain the environment-friendly enhanced alkali-free liquid accelerator.
The environmental-friendly enhanced alkali-free liquid accelerator prepared in the embodiment 1 to the embodiment 5 is tested, and the common portland cement of the sea snail P.O42.5 is selected. The obtained environment-friendly enhanced alkali-free liquid accelerator is subjected to cement paste setting time and cement mortar strength tests according to JC477-2005 accelerator for sprayed concrete. Wherein the dosage of the accelerator is calculated according to the percentage of the weight of the cement.
Cement paste setting time test
Cement 400
Water 160
Cement mortar Strength test
Cement 900
Standard sand 1350
Water 450
The accelerator is added to the cement slurry in an amount of 5% by weight of the cement, and the amount of water used includes water contained in the liquid accelerator. The setting time of the cement paste, the mortar strength and the stability were tested by using the currently commercially available alkali-free liquid accelerator (sample 1) as a comparison. The test results are shown in tables 1 and 2.
TABLE 1 Cement paste setting time test results
TABLE 2 Cement mortar Strength testing and stability
As can be seen from tables 1 and 2, the initial setting time and the final setting time of the environment-friendly enhanced alkali-free liquid accelerator are shorter than those of the commercially available alkali-free liquid accelerator, the ratio of the 1d compressive strength to the 28d compressive strength is higher, and the stability is better.
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
a preparation method of an environment-friendly enhanced alkali-free liquid accelerator comprises the following steps:
(1) acylation reaction: adding maleic anhydride and urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding a catalyst, slowly heating to 70-90 ℃, keeping the temperature for 1.5-4 hours, and cooling to obtain an acylation product, wherein the molar ratio of the maleic anhydride to the urea is 1: 1-2;
(2) preparation of suspension stabilizer: dripping the acylation product, acrylamide aqueous solution, acrylic acid aqueous solution, ammonium persulfate aqueous solution and molecular weight regulator aqueous solution into water for reaction, wherein the reaction temperature is 50-90 ℃, the dripping time is 1.0-4.0 h, and the heat preservation time is 0-3.0 h to obtain a suspension stabilizer; the total amount of water used in the step enables the mass concentration of the suspension stabilizer to be 5-40%, and the mass ratio of the acylation product, the acrylamide solution and the acrylic acid solution is 1: 1-2: 0.2-1;
(3) preparation of the reinforcing agent: reacting alcohol amine and oxalic acid at the reaction temperature of 50-90 ℃, adding a catalyst, and reacting for 1-4 hours to obtain a first mixture; adding glycerol into the first mixture to react at the temperature of 70-90 ℃ for 1-4h to obtain a reinforcing agent; the mol ratio of the alcohol amine to the oxalic acid to the glycerol is 1: 0.4-1.2; the alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, diethanol monoisopropanolamine and monoethanol diisopropanolamine;
the catalyst in the step (1) and the step (3) is p-toluenesulfonic acid and/or concentrated sulfuric acid;
(4) adding 0.2-3.0 parts by weight of the suspension stabilizer prepared in the step (2) and 1-10 parts by weight of the pH value regulator into water, stirring, reacting at 10-60 ℃, adding 30-60 parts by weight of aluminum sulfate, adding 1-20 parts by weight of the reinforcing agent prepared in the step (3) after 0.2-2.0 hours, and reacting for 0.2-1 hour to obtain the environment-friendly enhanced alkali-free liquid accelerator; the total amount of water used in the step enables the mass concentration of the environment-friendly enhanced alkali-free liquid accelerator to be 40-70%.
In the step (1), the amount of the catalyst is 0.3-0.6% of the total mass of the maleic anhydride and the urea. In the step (2), the using amount of the ammonium persulfate is 0.5-3.0% of the total mass of the acylation product, the acrylamide solution and the solute in the acrylic acid solution; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of solutes in the acylation product, the acrylamide solution and the acrylic acid solution. In the step (3), the dosage of the catalyst is 0.3-4.0% of the total mass of the alcohol amine and the oxalic acid.
The molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol and dodecanethiol. The pH value regulator is at least one of concentrated sulfuric acid, p-toluenesulfonic acid, citric acid, tartaric acid, salicylic acid and hydrofluoric acid.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (7)
1. A preparation method of an environment-friendly enhanced alkali-free liquid accelerator is characterized by comprising the following steps: the method comprises the following steps:
(1) acylation reaction: adding maleic anhydride and urea into a reaction device, heating to 60 ℃ under the protection of nitrogen, adding a catalyst, slowly heating to 70-90 ℃, keeping the temperature for 1.5-4 hours, and cooling to obtain an acylation product, wherein the molar ratio of the maleic anhydride to the urea is 1: 1-2;
(2) preparation of suspension stabilizer: dripping the acylation product, acrylamide aqueous solution, acrylic acid aqueous solution, ammonium persulfate aqueous solution and molecular weight regulator aqueous solution into water for reaction, wherein the reaction temperature is 50-90 ℃, the dripping time is 1.0-4.0 h, and the heat preservation time is 1.0-3.0 h to obtain a suspension stabilizer; the total amount of water used in the step enables the mass concentration of the suspension stabilizer to be 5-40%, and the mass ratio of the acylation product, the acrylamide aqueous solution and the acrylic acid aqueous solution is 1: 1-2: 0.2-1;
(3) preparation of the reinforcing agent: reacting alcohol amine and oxalic acid at the reaction temperature of 50-90 ℃, adding a catalyst, and reacting for 1-4 hours to obtain a first mixture; adding glycerol into the first mixture to react at the temperature of 70-90 ℃ for 1-4h to obtain a reinforcing agent; the molar ratio of the alcohol amine to the oxalic acid to the glycerol is 1:1: 0.4-1.2; the alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, diethanol monoisopropanolamine and monoethanol diisopropanolamine;
the catalyst in the step (1) and the step (3) is p-toluenesulfonic acid and/or concentrated sulfuric acid;
(4) adding 0.2-3.0 parts by weight of the suspension stabilizer prepared in the step (2) and 1-10 parts by weight of the pH value regulator into water, stirring, reacting at 10-60 ℃, adding 30-60 parts by weight of aluminum sulfate, adding 1-20 parts by weight of the reinforcing agent prepared in the step (3) after 0.2-2.0 hours, and reacting for 0.2-1 hour to obtain the environment-friendly enhanced alkali-free liquid accelerator; the total amount of water used in the step enables the mass concentration of the environment-friendly enhanced alkali-free liquid accelerator to be 40-70%.
2. The method of claim 1, wherein: in the step (1), the amount of the catalyst is 0.3-0.6% of the total mass of the maleic anhydride and the urea.
3. The method of claim 1, wherein: in the step (2), the use amount of the ammonium persulfate is 0.5-3.0% of the total mass of solutes in the acylation product, the acrylamide aqueous solution and the acrylic acid aqueous solution.
4. The method of claim 1, wherein: in the step (2), the amount of the molecular weight regulator is 0.2-3.0% of the total mass of solutes in the acylation product, the acrylamide aqueous solution and the acrylic acid aqueous solution.
5. The method of claim 1, wherein: in the step (3), the dosage of the catalyst is 0.3-4.0% of the total mass of the alcohol amine and the oxalic acid.
6. The production method according to any one of claims 1 to 5, characterized in that: the molecular weight regulator is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, isopropanol and dodecanethiol.
7. The production method according to any one of claims 1 to 5, characterized in that: the pH value regulator is at least one of concentrated sulfuric acid, p-toluenesulfonic acid, citric acid, tartaric acid, salicylic acid and hydrofluoric acid.
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| CN201810937456.9A CN109020292B (en) | 2018-08-16 | 2018-08-16 | Preparation method of environment-friendly enhanced alkali-free liquid accelerator |
| MYPI2019003975A MY192741A (en) | 2018-08-16 | 2019-05-08 | Method of preparing eco-friendly reinforced alkali-free liquid accelerators |
| PCT/CN2019/085963 WO2020034670A1 (en) | 2018-08-16 | 2019-05-08 | Preparation method for environmentally friendly reinforcement-type alkali-free liquid quick-setting agent |
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| CN109020292B (en) * | 2018-08-16 | 2020-04-10 | 科之杰新材料集团有限公司 | Preparation method of environment-friendly enhanced alkali-free liquid accelerator |
| CN109879631B (en) * | 2019-03-25 | 2021-08-31 | 科之杰新材料集团有限公司 | High-strength solubilizing liquid accelerator and preparation method thereof |
| CN113563004B (en) * | 2021-08-13 | 2022-05-17 | 科之杰新材料集团(贵州)有限公司 | Early strength agent and preparation method thereof |
| CN114956653B (en) * | 2022-03-15 | 2023-02-28 | 山西佳维新材料股份有限公司 | Coordination activator, liquid alkali-free accelerator and preparation method and application thereof |
| CN116161893B (en) * | 2023-03-02 | 2023-12-01 | 中国水利水电第七工程局有限公司 | Preparation method of crosslinking monomer for preparing high-early-strength low-resilience concrete |
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| CN108164175B (en) * | 2017-12-28 | 2020-05-15 | 浙江建研科之杰新材料有限公司 | Preparation method of low-alkali liquid accelerator |
| CN108101403B (en) * | 2017-12-28 | 2019-09-27 | 科之杰新材料集团有限公司 | A kind of preparation method of environment-friendly type alkali-free liquid accelerator |
| CN109020292B (en) * | 2018-08-16 | 2020-04-10 | 科之杰新材料集团有限公司 | Preparation method of environment-friendly enhanced alkali-free liquid accelerator |
-
2018
- 2018-08-16 CN CN201810937456.9A patent/CN109020292B/en active Active
-
2019
- 2019-05-08 MY MYPI2019003975A patent/MY192741A/en unknown
- 2019-05-08 WO PCT/CN2019/085963 patent/WO2020034670A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| MY192741A (en) | 2022-09-06 |
| CN109020292A (en) | 2018-12-18 |
| WO2020034670A1 (en) | 2020-02-20 |
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