CN115124271B - Cement grinding aid, preparation method thereof and cement - Google Patents

Cement grinding aid, preparation method thereof and cement Download PDF

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Publication number
CN115124271B
CN115124271B CN202210691199.1A CN202210691199A CN115124271B CN 115124271 B CN115124271 B CN 115124271B CN 202210691199 A CN202210691199 A CN 202210691199A CN 115124271 B CN115124271 B CN 115124271B
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parts
cement
grinding aid
grinding
cement grinding
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CN115124271A (en
Inventor
宋肖贤
苏晓强
边淑芳
石龙飞
只艳芳
安保灯
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Hebei Jinyu Dingxin Cement Co ltd
Tangshan Jidong Cement Admixture Co ltd
Bbmg Cement Co ltd
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Hebei Jinyu Dingxin Cement Co ltd
Tangshan Jidong Cement Admixture Co ltd
Bbmg Cement Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C04B2103/52—Grinding aids; Additives added during grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Disintegrating Or Milling (AREA)

Abstract

The application relates to the technical field of building materials, and particularly discloses a cement grinding aid, a preparation method thereof and cement. The cement grinding aid comprises the following raw materials in parts by weight: 30-40 parts of modified alcohol amine, 10-20 parts of sodium tripolyphosphate, 20-35 parts of para-aminophenol, 4-6 parts of sodium thiocyanate, 6-8 parts of nano negative ion powder and 60-80 parts of water; the preparation method comprises the following steps: all the raw materials were mixed. The cement produced by the cement grinding aid can reach 8.3-6.1% of screen residue with 45 mu m, the 3d compressive strength and the flexural strength can respectively reach 30.1-35.3MPa, 8.2-9.5MPa,28d compressive strength and flexural strength can respectively reach 53.5-62.8MPa and 9.7-11.2MPa, and the grinding effect is good and the cement strength is high.

Description

Cement grinding aid, preparation method thereof and cement
Technical Field
The application relates to the technical field of building materials, in particular to a cement grinding aid, a preparation method thereof and cement.
Background
Cement is a powdery hydraulic inorganic cementing material, is slurry after being added with water and stirred, can be hardened in air or water, can firmly bond sand, stone and other materials together, and is a common building material.
The main process of cement production technology is that raw materials are crushed to prepare raw materials, then the raw materials are sent into a high-temperature kiln to be calcined into mature materials by fuel, and finally the clinker and gypsum are mixed and ground to prepare cement.
Grinding aid is generally added in the cement grinding process, can reduce the electrostatic adsorption ball-coating phenomenon formed in the grinding process, can reduce the re-agglomeration trend of ultrafine particles formed in the grinding process, improves the cement fluidity, improves the grinding effect and reduces the grinding energy consumption.
At present, the multi-purpose grinding aid on the market is a single alcohol amine grinding aid or a compound alcohol amine grinding aid, and the applicant finds that the alcohol amine auxiliary agent can indeed improve the grinding effect and reduce the grinding energy consumption, but can cause the strength reduction of cement.
Disclosure of Invention
In order to improve the strength of cement while guaranteeing the grinding effect of cement, the application provides a cement grinding aid, a preparation method thereof and cement.
In a first aspect, the present application provides a cement grinding aid, which adopts the following technical scheme:
the cement grinding aid comprises the following raw materials in parts by weight: 30-40 parts of modified alcohol amine, 10-20 parts of sodium tripolyphosphate, 20-35 parts of p-aminophenol, 4-6 parts of sodium thiocyanate, 6-8 parts of nano negative ion powder and 60-80 parts of water.
By adopting the technical scheme, the modified alcohol amine reacts with C through acid-base acting force 3 A and C 4 Al on AF surface 3+ 、Fe 3+ The plasma cation groups are selectively bonded, unsaturated charges are neutralized through adsorption, the surface energy of powder particles is reduced, and the particles are prevented from mutually approaching to each other to be agglomerated and the section is prevented from healing; sodium tripolyphosphate molecules react with Ca on the mineral phase surface of cement particles through acid-base action force 2+ 、Al 3+ And Fe (Fe) 3+ Complexing to form stable coordinated octahedral structureThe rest two unsaturated bond-forming O in the particles extend to the outside, so that the polar surface energy, the duty ratio and the alkalinity constant of the polar surface energy are obviously increased, and the mutual approaching and agglomeration of the polar surface energy and the duty ratio and the alkalinity constant are prevented by the mutual electric repulsion between particles; and, free Na in sodium tripolyphosphate + Will enter into the lattice cavity or with Ca in the lattice 2+ The replacement effect is generated, so that the lattice distortion of minerals is further aggravated, the fracture of chemical bonds in the mineral materials is accelerated, the modified alcohol amine and the sodium tripolyphosphate are mutually cooperated before, the agglomeration of cement clinker particles is reduced, and the grinding effect is improved.
The modified alcohol amine and the para-aminophenol have an improvement effect on the fineness of the powder particles within the range defined by the application, so that the fineness is finer, and meanwhile, the cement strength can be increased, and the later strength of the cement is obviously improved; sodium thiocyanate is an early strength agent, and sodium thiocyanate and aminophenol are added into the grinding aid to improve the early strength and the later strength of cement. The nano negative ion powder can reduce the surface tension of the grinding powder slurry, so that modified alcohol amine, sodium tripolyphosphate, para-aminophenol and sodium thiocyanate can better enter the grinding powder slurry to exert the effect, and further improve the grinding effect and the cement strength.
Preferably, the preparation method of the modified alcohol amine comprises the following steps:
1) Synthesizing an intermediate by the reaction of maleic anhydride and triethanolamine;
2) Carrying out polymerization reaction on the intermediate obtained in the step 1) and maleic anhydride, methacrylic acid and methallyl alcohol polyoxyethylene ether under the action of a chain transfer agent and an initiator to obtain a reaction liquid, and then regulating the pH value of the reaction liquid to be 6-8 by using a pH regulator to obtain modified alcohol amine, wherein the molar ratio of the intermediate, the maleic anhydride, the methacrylic acid and the methallyl alcohol polyoxyethylene ether is as follows: (2-3): (1-2): 1:1.
Through adopting the technical scheme, molecular structure design and adjustment are carried out through free radical polymerization reaction, functional groups are introduced on alcohol amine, and the obtained modified alcohol amine can be subjected to physical adsorption or chelation reaction with silicon aluminide on the surface of cement clinker, so that uniform particle substances are formed on the surface, the surface energy is increased, collision in the grinding process of clinker particles is facilitated, the grinding effect is improved, the cement particle grading is improved, and the cement strength is improved.
Preferably, the initiator is used in an amount of 2-3% of the total weight of maleic anhydride, methacrylic acid and methallyl alcohol polyoxyethylene ether.
Preferably, the relative molecular weight of the methallyl alcohol polyoxyethylene ether is 400-1500.
By adopting the technical scheme, the initiator can influence the monomer conversion rate, the initiator has higher monomer conversion rate within the range limited by the application, and the obtained modified alcohol amine has better grinding assisting performance; if the initiator content is too low, it may result in low monomer conversion; if the content of the initiator is too high, the reaction speed is possibly too high, the branched chains of the polymer molecules are increased, a random coil conformation appears, polar groups such as hydroxyl groups in a shielding molecular chain and the like are shielded, the polymerization degree is reduced, and the grinding assisting function of the modified alcohol amine is reduced.
Preferably, the weight ratio of the modified alcohol amine to the para-aminophenol is (1-1.5): 1.
by adopting the technical scheme, the proportion of the modified alcohol amine and the para-aminophenol is limited, the grinding assisting effect of the para-aminophenol is not obvious, but the para-aminophenol can assist the modified alcohol amine to exert the grinding assisting effect, so that the grinding assisting effect is further improved, and the specific surface area of the grinding particles is improved; in addition, the strength of the cement can be improved by compounding the para-aminophenol and the modified alcohol amine, and the effect of improving the later strength of the cement is more obvious in the proportioning range limited by the application.
Preferably, it further comprises 20-30 parts by weight of calcium lignosulfonate.
By adopting the technical scheme, the calcium lignosulfonate has surface activity, so that the surface tension of the grinding powder slurry can be reduced, substances such as modified alcohol amine and the like can be promoted to enter the grinding powder slurry, and the functions are fully exerted; the calcium lignosulfonate molecular mechanism contains polar functional groups such as carboxyl, phenolic hydroxyl and the like, can be adsorbed on the surface of cement clinker, and plays a certain grinding-assisting effect; in the grinding process, calcium lignosulfonate molecules are firstly adsorbed on the powderOn the high-energy surface of the material, the energy density and the strength of the broken surface of the particles are reduced along with the continuous expansion of the cracks of the particles, calcium lignosulfonate molecules further permeate into the cracks to play a role in preventing the reclosing of the powder cracks, so that the grinding efficiency is increased, and the fineness of the materials such as clinker is reduced under the same grinding time. Calcium ions contained in the molecular structure of calcium lignosulfonate have strong charge and are used for Ca on fracture surfaces formed in the collision process of clinker + The rejection capability of the active points is stronger, and the grinding assisting effect is improved.
Preferably, it further comprises 8-10 parts by weight of calcium formate.
By adopting the technical scheme, the calcium formate can accelerate the hardening speed of cement, improve the early strength, and the calcium formate is matched with the modified alcohol amine, so that the strength of cement is improved, the grinding effect can be improved, and the fineness of cement particles is improved.
In a second aspect, the present application provides a method for preparing a cement grinding aid, which adopts the following technical scheme:
the preparation method of the cement grinding aid comprises the following steps: weighing the raw materials according to the weight parts, and uniformly mixing the raw materials.
Preferably, the method comprises the following steps:
s1, weighing calcium formate and water according to parts by weight, and dissolving the calcium formate in the water to obtain a calcium formate solution;
s2, weighing other raw materials according to parts by weight, adding the raw materials into the calcium formate solution obtained in the step S1, and uniformly mixing to obtain the cement grinding aid.
By adopting the technical scheme, the method is simple to operate, has no special requirement on the most production equipment, and is suitable for industrial development.
In a second aspect, the present application provides a cement produced using any of the cement grinding aids described above.
In summary, the present application has the following beneficial effects:
1. because the modified alcohol amine is compounded with sodium tripolyphosphate, para-aminophenol, sodium thiocyanate and nano negative ion powder as the grinding aid, the nano negative ion powder reduces the surface tension of the grinding powder slurry, so that the modified alcohol amine, sodium tripolyphosphate, para-aminophenol and sodium thiocyanate can better enter the grinding powder slurry, the modified alcohol amine and the sodium tripolyphosphate are combined with minerals in the grinding powder slurry system through the action of acid and alkali, agglomeration among particles is prevented, the grinding effect is improved, and meanwhile, the strength of cement is improved under the combined action of the para-aminophenol and the sodium thiocyanate; the screen residue of the produced cement with 45 mu m can reach 8.3-6.1%, the compressive strength of 3d can reach 30.1-35.3MPa, the compressive strength of 8.2-9.5MPa, and the flexural strength of 28d can reach 53.5-62.8MPa, and the flexural strength of 9.7-11.2MPa respectively.
2. In the application, calcium lignosulfonate is preferably added, the 45 mu m screen residue of the produced cement can reach 6.9-6.1%, the 3d compressive strength and the flexural strength can respectively reach 32.8-35.3MPa, 8.9-9.5MPa,28d compressive strength and flexural strength can respectively reach 58.3-62.8MPa and 10.5-11.2MPa, and the grinding effect and the cement strength of the cement are further improved.
Detailed Description
The present application is described in further detail below with reference to examples.
Preparation examples of starting materials and intermediates
Raw materials
The nanometer negative ion powder is of industrial grade;
the catalyst is p-toluenesulfonic acid;
the initiator is ammonium persulfate;
the pH regulator is sodium hydroxide.
Preparation example
Preparation example 1
A preparation method of the modified alcohol amine comprises the following steps:
1) The maleic anhydride and the triethanolamine are reacted under the action of a catalyst to synthesize an intermediate, wherein the reaction temperature is 110 ℃, the reaction time is 3 hours, and the molar ratio of the maleic anhydride to the triethanolamine is 1.5:1;
2) The molar ratio of the intermediate, the maleic anhydride, the methacrylic acid and the methallyl alcohol polyoxyethylene ether is as follows: 2:2:1:1, mixing materials with the amount of an initiator being 2% of the total weight of maleic anhydride, methacrylic acid and methallyl alcohol polyoxyethylene ether; uniformly mixing the intermediate with maleic anhydride and methallyl alcohol polyoxyethylene ether to obtain a primary mixed solution; simultaneously dripping methacrylic acid and an initiator into the primary mixed solution, wherein the dripping time of the methacrylic acid is controlled to be 1.5h, the dripping time of the initiator is 15min more than that of the methacrylic acid, and the dripping temperature is 70 ℃; after the dripping is completed, reacting for 3 hours at 70 ℃ to obtain a reaction liquid, and then regulating the pH value of the reaction liquid to 7 by using a pH regulator to obtain modified alcohol amine; wherein the relative molecular weight of the methallyl alcohol polyoxyethylene ether is 400.
Preparation example 2
Unlike in preparation example 1, the molar ratio of maleic anhydride, methacrylic acid, methallyl alcohol polyoxyethylene ether in preparation example 2 is: 3:1:1:1.
preparation example 3
Unlike in preparation example 1, the amount of the initiator in preparation example 3 was 3% by weight based on the total weight of maleic anhydride, methacrylic acid and methallyl alcohol polyoxyethylene ether.
Preparation example 4
Unlike in preparation example 1, the amount of the initiator in preparation example 4 was 4% by weight based on the total weight of maleic anhydride, methacrylic acid and methallyl alcohol polyoxyethylene ether.
Preparation example 5
Unlike in preparation example 1, the relative molecular weight of methallyl alcohol polyoxyethylene ether in preparation example 5 was 1500.
Examples
Examples 1 to 5
A cement grinding aid comprises the following preparation methods:
according to the raw material proportions in table 1, the raw materials are uniformly mixed to obtain the cement grinding aid, wherein the modified alcohol amine is from preparation example 1.
Examples 6 to 8
In contrast to example 4, the starting materials in examples 6 to 8 also comprise calcium lignosulfonate, as detailed in Table 1, and were prepared in the same way as in example 4.
Examples 9 to 11
Unlike example 7, the starting materials in examples 9-11 also included calcium formate, as detailed in Table 1, were prepared by:
s1, weighing calcium formate and water according to the proportion of the table 1, and dissolving the calcium formate in the water to obtain a calcium formate solution;
s2, weighing other raw materials according to the proportion of the table 1, adding the raw materials into the calcium formate solution obtained in the step S1, and uniformly mixing to obtain the cement grinding aid.
Table 1 examples 1-11 raw materials proportioning Table (kg)
Examples 12 to 15
Unlike example 10, the modified alcohol amines in examples 12 to 15 were derived from preparation examples 2 to 5, respectively.
Comparative example
Comparative example 1
Unlike example 1, comparative example 1 replaced sodium tripolyphosphate with an equivalent amount of modified alcohol amine.
Comparative example 2
Unlike example 1, comparative example 2 replaced para-aminophenol with an equivalent amount of modified alcohol amine.
Comparative example 3
Unlike example 1, sodium thiocyanate was replaced with an equal amount of sodium tripolyphosphate in comparative example 3.
Comparative example 4
Unlike example 1, comparative example 4 does not contain nano negative ion powder.
Application example
Application example 1
A cement is prepared by the following steps:
58kg of cement clinker, 4kg of gypsum, 23kg of limestone, 4kg of high silica sand rock, 1kg of manganese slag and 10kg of furnace bottom slag are uniformly mixed, and then 0.05kg of cement grinding aid obtained in example 1 is added for grinding into cement.
Application examples 2 to 15
Unlike application example 1, the cement grinding aids in application examples 2 to 15 were derived from examples 2 to 16, respectively.
Comparative application examples 1 to 4
Unlike application example 1, the cement grinding aids in comparative application examples 1 to 4 are derived from comparative examples 1 to 4, respectively.
Performance test
Detection method/test method
The compressive strength, flexural strength and 45 μm screen residue of the cements of application examples 1 to 15 and comparative application examples 1 to 4 were examined according to general Portland Cement GB175-2020, and the examination results are shown in Table 2.
TABLE 2 Performance test results
As can be seen from the combination of the application examples 1 to 15 and the comparative application examples 1 to 4 and the combination of Table 2, the 45 μm screen residue in the application examples 1 to 15 is lower than that in the comparative application examples 1 to 4, which indicates that the fineness of the cement particles in the present application is finer and the grinding effect is better; the 3d strength and 28d strength of application examples 1-15 are both higher than those of comparative application examples 1-4, indicating that the cement produced by grinding with the cement grinding aid of the present application is higher in strength. The cement grinding aid can improve the grinding effect of cement particles and the strength of cement.
As can be seen from the combination of application examples 1 and comparative application examples 1 to 4 and the combination of table 2, the raw materials of the cement grinding aid in comparative application examples 1 to 4 lack sodium tripolyphosphate, para-aminophenol, sodium thiocyanate and nano negative ion powder respectively, so that the fineness of cement and the strength of cement in comparative application examples 1 to 4 are obviously reduced compared with those in application example 1, and the reason is that the nano negative ion powder in the application reduces the surface tension of the grinding powder slurry, so that modified alcohol amine, sodium tripolyphosphate, para-aminophenol and sodium thiocyanate can better enter the grinding powder slurry, and the modified alcohol amine and sodium tripolyphosphate are combined with minerals in the grinding powder slurry system through the action of acid and alkali to prevent agglomeration among particles, so that the grinding effect is improved, and meanwhile, the strength of cement is improved under the combined action of para-aminophenol and sodium thiocyanate.
As can be seen from the combination of application examples 1 to 5 and the combination of table 2, the mixing ratio of the modified alcohol amine and the para-aminophenol affects the grinding effect of the cement particles and the cement strength, wherein the grinding effect of the cement particles and the cement strength are better in the application examples 3 and the application examples 4 to 5, which indicates that the mixing ratio of the modified alcohol amine and the para-aminophenol is (1 to 1.5): and 1, the overall effect is better.
As can be seen from the combination of application examples 4 and 6-8 and the combination of table 2, the cement in application examples 6-8 is better in particle fineness and strength, probably because calcium lignosulfonate reduces surface tension of grinding slurry, promotes substances such as modified alcohol amine and the like to enter the grinding slurry, and simultaneously calcium lignosulfonate molecules can be adsorbed on the surface of cement clinker.
It can be seen from the combination of application examples 10 and 13 to 14 and the combination of Table 2 that the content of the initiator has a certain influence on the grinding effect, probably because the monomer conversion rate is increased with the increase of the addition amount of the initiator, and the grinding assisting performance of the obtained modified alcohol amine is better; however, when the addition amount of the initiator exceeds the range defined in the application, the reaction speed is too high, the branched chains of the polymer molecules are increased, a random coil conformation appears, polar groups such as hydroxyl groups in the shielding molecular chain and the like are shielded, so that the polymerization degree is reduced, and the grinding assisting function of the modified alcohol amine is reduced.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (6)

1. The cement grinding aid is characterized by comprising the following raw materials in parts by weight: 30-40 parts of modified alcohol amine, 10-20 parts of sodium tripolyphosphate, 20-35 parts of para-aminophenol, 4-6 parts of sodium thiocyanate, 6-8 parts of nano negative ion powder, 60-80 parts of water, 30 parts of calcium lignosulfonate and 10 parts of calcium formate;
the preparation method of the modified alcohol amine comprises the following steps:
1) Synthesizing an intermediate by the reaction of maleic anhydride and triethanolamine;
2) Carrying out polymerization reaction on the intermediate obtained in the step 1) and maleic anhydride, methacrylic acid and methallyl alcohol polyoxyethylene ether under the action of a chain transfer agent and an initiator to obtain a reaction liquid, and then regulating the pH value of the reaction liquid to be 6-8 by using a pH regulator to obtain modified alcohol amine, wherein the molar ratio of the intermediate, the maleic anhydride, the methacrylic acid and the methallyl alcohol polyoxyethylene ether is as follows: 3:1:1:1.
2. a cement grinding aid as claimed in claim 1, wherein: the amount of the initiator is 2-3% of the total weight of the maleic anhydride, the methacrylic acid and the methallyl alcohol polyoxyethylene ether.
3. A cement grinding aid as claimed in claim 1, wherein: the relative molecular weight of the methallyl alcohol polyoxyethylene ether is 400-1500.
4. A cement grinding aid as claimed in claim 1, wherein: the weight ratio of the modified alcohol amine to the para-aminophenol is (1-1.5): 1.
5. a method for preparing the cement grinding aid as claimed in claim 1, comprising the steps of:
s1, weighing calcium formate and water according to parts by weight, and dissolving the calcium formate in the water to obtain a calcium formate solution;
s2, weighing other raw materials according to parts by weight, adding the raw materials into the calcium formate solution obtained in the step S1, and uniformly mixing to obtain the cement grinding aid.
6. A cement produced using the cement grinding aid of any one of claims 1-4.
CN202210691199.1A 2022-06-18 2022-06-18 Cement grinding aid, preparation method thereof and cement Active CN115124271B (en)

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CN115872664B (en) * 2023-01-17 2023-05-12 慧力达(天津)科技发展有限公司 Environment-friendly enhanced high-performance cement grinding aid and preparation method thereof
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CN112456855A (en) * 2020-12-14 2021-03-09 山东天汇科技有限公司 Liquid grinding aid for improving later strength of cement and preparation method thereof
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