High-performance grinding aid for superfine composite mineral admixture and preparation method thereof

Abstract

The application discloses a high-performance grinding aid for superfine composite mineral admixture and a preparation method thereof. The grinding aid is composed of the following components in percentage by weight: polyamine carboxylic acid polymer 35-50%, modified nano-silica 5-15%, polyol derivative 15-30%, and alcohol amine derivative 15-30%. The application utilizes the adsorption and dispersion of the polyamine carboxylic acid polymer, the particle skeleton and multi-level filling of the modified nano-silica, the crack penetration of the polyol derivative and the alcohol amine, and the charge neutralization and polymerization inhibition of the polar groups such as amine groups, hydroxyl groups and carboxyl groups in the components to form a synergistic grinding combination. Compared with traditional grinding aids, the grinding aid is more conducive to the extrusion, crushing and dispersion of particles, can effectively prevent the particles from being pasted on the surface of the grinding ball, has better grinding effect, higher grinding efficiency and more stable grinding performance.

Description

Technical Field

[0001] This invention relates to the field of concrete technology. More specifically, this invention relates to high-performance grinding aids for ultrafine composite mineral admixtures and their preparation methods. Background Technology

[0002] Mineral admixtures, as a key component of concrete, effectively improve its workability, thermodynamic properties, and durability. Commonly used mineral admixtures include fly ash, mineral powder, silica fume, and limestone powder. Except for silica fume, other admixtures can be further ground to produce ultrafine admixtures such as fly ash microspheres, ultrafine mineral powder, and ultrafine limestone powder. These admixtures exhibit enhanced chemical activity and specific surface areas exceeding 600 m². 2 / kg, which can be used to prepare high-performance or ultra-high-performance concrete. In addition, some construction solid wastes such as waste bricks and waste structural concrete, as well as some industrial solid wastes such as steel slag, red mud, rice husk ash, phosphorus slag, iron tailings slag, copper tailings slag, molybdenum tailings slag, glass slag, lithium slag, titanium slag, pyrite cinder, calcium carbide slag, nickel slag, manganese slag, ferrosilicon slag, vanadium-titanium slag, and lead-zinc tailings slag also have potential hydration characteristics. After multi-component ultrafine grinding, ultrafine composite mineral admixtures can be prepared and applied to concrete, thereby greatly improving the resource utilization rate of solid waste and truly realizing "turning waste into treasure".

[0003] However, the ultrafine grinding processes for commonly used mineral admixtures and construction and industrial solid waste place higher demands on grinding aids. Traditional grinding aids, such as triethanolamine, ethylene glycol, calcium lignosulfonate, molasses, polyphosphates, and gypsum, are mostly used in cement grinding and have poor performance stability. Their effects vary depending on different cement clinker, affecting the stability and durability of cement, and they have poor compatibility with other concrete admixtures such as water-reducing agents. Furthermore, traditional grinding aids used in ultrafine grinding processes are prone to particle agglomeration and sticking to the surface of grinding balls, resulting in limited grinding aid effects, high energy consumption, and low grinding efficiency. Moreover, due to the complex composition and varying wear resistance of construction and industrial solid waste, traditional grinding aids are even more difficult to apply. Therefore, there is an urgent need to develop a high-performance grinding aid suitable for ultrafine composite mineral admixtures. This grinding aid should not only be applicable to the ultrafine grinding of cement, commonly used mineral admixtures, and construction and industrial solid waste, but also be less prone to ball sticking, have good grinding aid effects, high grinding efficiency, and stable grinding performance. Summary of the Invention

[0004] One objective of this invention is to provide a high-performance grinding aid for ultrafine composite mineral admixtures and its preparation method, which is not only suitable for ultrafine grinding of cement and commonly used mineral admixtures as well as construction and industrial solid waste, but also has the advantages of being less prone to balling, having good grinding aid effect, high grinding efficiency, and stable grinding performance.

[0005] To solve the above-mentioned technical problems, the present invention provides a high-performance grinding aid for ultrafine composite mineral admixtures, comprising the following components by weight percentage: 35-50% polyamine carboxylic acid polymer, 5-15% modified nano silica, 15-30% polyol derivative, and 15-30% alkanolamine derivative.

[0006] Preferably, the polyamine carboxylic acid polymer is prepared according to the following steps:

[0007] 1) Add organic polyamine to the reactor, stir and purge with nitrogen, then add maleic anhydride, seal the reactor opening, heat to 50°C and start heat preservation, and control the cooling water to ensure that the temperature inside the reactor is between 55-70°C for 1 hour. Finally, cool down to below 45°C, turn off the nitrogen and cooling water to obtain maleic polyamine monomer for later use.

[0008] 2) Add polyether macromonomer and deionized water to another reactor. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1-2 hours, and the holding time is 1-1.5 hours. After the holding time is completed, spray dry to obtain powdered polyamine carboxylic acid polymer.

[0009] Preferably, the organic polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; and the polyether macromonomer is one or more of methyl allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, ethylene glycol monovinyl polyoxyethylene ether, and 4-hydroxybutyl polyoxyethylene ether with relative molecular masses of 400, 600, 800, 1000, and 1200.

[0010] Preferably, the molar ratio of maleic anhydride to organic polyamine is 1:1.05; and the molar ratio of polyether macromonomer, acrylic acid, maleic polyamine monomer, hydrogen peroxide, ascorbic acid, and mercaptopropionic acid is 1:(1.0-2.5):(0.1-0.2):(0.04-0.18):(0.005-0.02):(0.03-0.15).

[0011] Preferably, the modified nano-silica is prepared by the following steps: adding nano-silica and xylene to a reaction vessel, stirring and purging with nitrogen, heating to 80°C and adding a silane modifier, maintaining the temperature for 4 hours, then adding p-toluenesulfonic acid, heating to 150°C and adding a branching modifier, and continuing to maintain the temperature for 2 hours; after the temperature-maintaining reaction is completed, cooling to room temperature, and finally centrifuging and drying to obtain the modified nano-silica.

[0012] Preferably, the nano-silica is one or more of nano-silica with a purity > 99.5%, hydroxyl content > 45%, and average particle size of 15nm, 20nm, 30nm, 50nm, and 80nm; the silane modifier is one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, diethylenetriaminopropyltriethoxysilane, and diethylaminomethyltriethoxysilane; the branching modifier is one or more of 2,2-bis(hydroxymethyl)propionic acid, 2,2-dihydroxymethylbutyric acid, and (R)-3-amino-2-(hydroxymethyl)propionic acid.

[0013] Preferably, the molar ratio of the nano-silica, silane modifier, branching modifier, and p-toluenesulfonic acid is 7:3:3:0.015.

[0014] Preferably, the polyol derivative is one or more of 2-hydroxymethyl-1,3-propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-di(2-hydroxyethyl)amino-2-hydroxymethyl-1,3-propanediol, aminobutanetriol, 2,2-dihydroxymethylbutanol, and 1,3-bis(hydroxymethyl)urea.

[0015] Preferably, the alcohol amine derivative is one or more of N-(hydroxymethyl)ethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-nitrosodiethanolamine, N-(3-aminopropyl)diethanolamine, N-acetylethanolamine, and diethanol monoisopropanolamine.

[0016] This invention also provides a method for preparing a high-performance grinding aid for ultrafine composite mineral admixtures, which is prepared by the following steps: adding polyol derivatives and alkanolamine derivatives to a mixing tank, stirring for 30 min, adding modified nano-silica, continuing to stir for 30 min, and finally adding polyamine carboxylic acid polymer and continuing to stir for 1 h to obtain the high-performance grinding aid for ultrafine composite mineral admixtures.

[0017] The present invention has at least the following beneficial effects:

[0018] (1) The polyamine carboxylic acid polymer in the high-performance grinding aid contains a large number of polar groups such as amine and carboxyl groups, which can neutralize the static charge of the newly formed cross-sectional area of ​​the particles, thereby shielding the attraction and weakening the particle agglomeration; at the same time, the polymer can be adsorbed on the particle surface and disperse the particles through the steric hindrance of the polymer, further preventing agglomeration, and can also effectively prevent the particles from sticking to the surface of the grinding ball.

[0019] (2) The modified nano silica in the high-performance grinding aid not only has a hard particle skeleton, which can act as a grinding body to help the particles squeeze, collide and break, but also effectively prevents the particles from sticking to the surface of the grinding ball. Moreover, its surface also has a large number of polar groups such as hydroxyl and amino groups, which can also play a certain role in inhibiting polymerization. Finally, the modified nano silica with different particle sizes can be used to form a multi-grade filling, reduce the gap between particles, and make it more conducive to the squeezing and breaking of particles.

[0020] (3) The polyol derivatives and alcohol amine derivatives in the high-performance grinding aid components are small organic molecules and contain a large number of polar groups such as hydroxyl and amine groups. In addition to eliminating the static charge of the newly formed cross-section of the particles and preventing the particles from agglomerating, they can also penetrate into the cracks of the newly formed cross-section, reduce the stress required for crack propagation, accelerate the generation of cracks, and thus improve grinding efficiency.

[0021] (4) The high-performance grinding aid fully utilizes the adsorption and dispersion effect of polyamine carboxylic acid polymer, the particle skeleton and multi-gradation filling effect of modified nano silica, the crack penetration effect of polyol derivatives and alkanolamines, and the charge neutralization and polymerization inhibition effect of polar groups such as amine, hydroxyl and carboxyl groups in each component, forming a synergistic grinding aid combination. Compared with traditional grinding aids, it is more conducive to the extrusion, crushing and dispersion of particles, and can also effectively prevent particles from sticking to the surface of grinding balls, resulting in better grinding effect, higher grinding efficiency and more stable grinding performance.

[0022] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Detailed Implementation

[0023] To better understand the purpose, structure, and function of this invention, the following detailed description is provided in conjunction with embodiments, so that those skilled in the art can implement it based on the description.

[0024] It should be noted that, unless otherwise specified, the experimental methods described in the following implementation plan are all conventional methods, and the reagents and materials described are all commercially available unless otherwise specified.

[0025] Example 1

[0026] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0027] (1) Preparation of polyamine carboxylic acid polymers:

[0028] 1) Add ethylenediamine to the reactor, stir and purge with nitrogen, then add maleic anhydride, seal the reactor opening, heat to 50°C and start holding at that temperature, and control the cooling water to ensure that the temperature inside the reactor is between 55-70°C for 1 hour. Finally, cool down to below 45°C, turn off the nitrogen and cooling water, and obtain maleic polyamine monomer for later use; wherein the molar ratio of maleic anhydride to ethylenediamine is 1:1.05.

[0029] 2) In another reactor, add methyl allyl polyoxyethylene ether with a relative molecular weight of 400 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1 hour, and the holding time is 1.5 hours. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of methyl allyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1:0.1:0.04:0.005:0.03.

[0030] (2) Preparation of modified nano silica: Nano silica with an average particle size of 15 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and 3-aminopropyltrimethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, then p-toluenesulfonic acid was added, the temperature was raised to 150 °C, 2,2-bis(hydroxymethyl)propionic acid was added, and the reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, 3-aminopropyltrimethoxysilane, 2,2-bis(hydroxymethyl)propionic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0031] (3) Preparation of high-performance grinding aid: Add 20% by weight of 2-hydroxymethyl-1,3-propanediol and 30% by weight of N-(hydroxymethyl)ethanolamine to a mixing tank, stir for 30 min, add 15% by weight of modified nano-silica, continue stirring for 30 min, and finally add 35% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-1 for ultrafine composite mineral admixture.

[0032] Example 2

[0033] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0034] (1) Preparation of polyamine carboxylic acid polymers:

[0035] 1) Add diethylenetriamine to the reactor, stir and purge with nitrogen, then add maleic anhydride, seal the reactor opening, heat to 50°C and start holding at that temperature, and control the cooling water to ensure that the temperature inside the reactor is between 55-70°C for 1 hour. Finally, cool down to below 45°C, turn off the nitrogen and cooling water, and obtain maleic polyamine monomer for later use; wherein the molar ratio of maleic anhydride to diethylenetriamine is 1:1.05.

[0036] 2) In another reactor, add isopentenyl polyoxyethylene ether with a relative molecular weight of 600 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1.5 h, and the holding time is 1.5 h. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of isopentenyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1:0.15:0.08:0.008:0.07.

[0037] (2) Preparation of modified nano silica: Nano silica with an average particle size of 20 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and 3-aminopropyltriethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at this temperature for 4 h, and then p-toluenesulfonic acid was added. The temperature was raised to 150 °C, and 2,2-dihydroxymethylbutyric acid was added. The reaction was kept at this temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, 3-aminopropyltriethoxysilane, 2,2-dihydroxymethylbutyric acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0038] (3) Preparation of high-performance grinding aid: Add 30% by weight of 2-hydroxymethyl-2-methyl-1,3-propanediol and 20% by weight of N-methyldiethanolamine to a mixing tank, stir for 30 min, add 10% by weight of modified nano-silica, continue stirring for 30 min, and finally add 40% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-2 for ultrafine composite mineral admixture.

[0039] Example 3

[0040] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0041] (1) Preparation of polyamine carboxylic acid polymers:

[0042] 1) Add triethylenetetramine to the reactor, stir and purge with nitrogen, then add maleic anhydride, seal the reactor opening, heat to 50°C and start holding at that temperature, and control the cooling water to ensure that the temperature inside the reactor is between 55-70°C for 1 hour. Finally, cool down to below 45°C, turn off the nitrogen and cooling water, and obtain maleic polyamine monomer for later use; wherein the molar ratio of maleic anhydride to triethylenetetramine is 1:1.05.

[0043] 2) In another reactor, add ethylene glycol monovinyl polyoxyethylene ether with a relative molecular weight of 800 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1 hour, and the holding time is 1.5 hours. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of ethylene glycol monovinyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1.5:0.1:0.06:0.006:0.05.

[0044] (2) Preparation of modified nano silica: Nano silica with an average particle size of 30 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and 3-aminopropylmethyldimethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, and then p-toluenesulfonic acid was added. The temperature was raised to 150 °C, and (R)-3-amino-2-(hydroxymethyl)propionic acid was added. The reaction was kept at the temperature for 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, 3-aminopropylmethyldimethoxysilane, (R)-3-amino-2-(hydroxymethyl)propionic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0045] (3) Preparation of high-performance grinding aid: 20% by weight of 2-di(2-hydroxyethyl)amino-2-hydroxymethyl-1,3-propanediol and 30% by weight of N-ethyldiethanolamine were added to the mixing tank and stirred for 30 min. Then, 5% by weight of modified nano-silica was added and stirred for another 30 min. Finally, 45% by weight of polyamine carboxylic acid polymer was added and stirred for another 1 h to obtain high-performance grinding aid ZM-3 for ultrafine composite mineral admixture.

[0046] Example 4

[0047] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0048] (1) Preparation of polyamine carboxylic acid polymers:

[0049] 1) Add tetraethylenepentamine to the reactor, stir and purge with nitrogen, then add maleic anhydride, seal the reactor opening, heat to 50°C and start holding at that temperature, and control the cooling water to ensure that the temperature inside the reactor is between 55-70°C for 1 hour. Finally, cool down to below 45°C, turn off the nitrogen and cooling water, and obtain maleic polyamine monomer for later use; wherein the molar ratio of maleic anhydride to tetraethylenepentamine is 1:1.05.

[0050] 2) In another reactor, add 4-hydroxybutyl polyoxyethylene ether with a relative molecular weight of 1000 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1.5 h, and the holding time is 1 h. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of 4-hydroxybutyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1.5:0.15:0.1:0.01:0.08.

[0051] (2) Preparation of modified nano silica: Nano silica with an average particle size of 50 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and 3-aminopropylmethyldiethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, then p-toluenesulfonic acid was added, the temperature was raised to 150 °C, 2,2-bis(hydroxymethyl)propionic acid was added, and the reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, 3-aminopropylmethyldiethoxysilane, 2,2-bis(hydroxymethyl)propionic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0052] (3) Preparation of high-performance grinding aid: Add 25% by weight of aminobutanetriol and 15% by weight of N-propyldiethanolamine to the mixing tank, stir for 30 min, add 10% by weight of modified nano-silica, continue stirring for 30 min, and finally add 50% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-4 for ultrafine composite mineral admixture.

[0053] Example 5

[0054] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0055] (1) Preparation of polyamine carboxylic acid polymers:

[0056] 1) Same as Example 1.

[0057] 2) In another reactor, add methyl allyl polyoxyethylene ether with a relative molecular weight of 1200 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 2 hours, and the holding time is 1.5 hours. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of methyl allyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1.5:0.2:0.15:0.012:0.1.

[0058] (2) Preparation of modified nano silica: Nano silica with an average particle size of 80 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, then p-toluenesulfonic acid was added, the temperature was raised to 150 °C, 2,2-dihydroxymethylbutyric acid was added, and the reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 2,2-dihydroxymethylbutyric acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0059] (3) Preparation of high-performance grinding aid: Add 30% by weight of 2,2-dimethylolbutanol and 25% by weight of N-butyldiethanolamine to a mixing tank, stir for 30 min, add 10% by weight of modified nano-silica, continue stirring for 30 min, and finally add 35% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-5 for ultrafine composite mineral admixture.

[0060] Example 6

[0061] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0062] (1) Preparation of polyamine carboxylic acid polymers:

[0063] 1) Same as Example 2.

[0064] 2) In another reactor, add isopentenyl polyoxyethylene ether with a relative molecular weight of 400 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1.5 h, and the holding time is 1 h. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of isopentenyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1.8:0.1:0.08:0.05:0.03.

[0065] (2) Preparation of modified nano silica: Nano silica with an average particle size of 15 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, and then p-toluenesulfonic acid was added. The temperature was raised to 150 °C, and (R)-3-amino-2-(hydroxymethyl)propionic acid was added. The reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, (R)-3-amino-2-(hydroxymethyl)propionic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0066] (3) Preparation of high-performance grinding aid: Add 25% by weight of 1,3-bis(hydroxymethyl)urea and 30% by weight of N-nitrosodiethanolamine to a mixing tank, stir for 30 min, add 5% by weight of modified nano-silica, continue stirring for 30 min, and finally add 40% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-6 for ultrafine composite mineral admixture.

[0067] Example 7

[0068] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0069] (1) Preparation of polyamine carboxylic acid polymers:

[0070] 1) Same as Example 3.

[0071] 2) In another reactor, add ethylene glycol monovinyl polyoxyethylene ether with a relative molecular weight of 600 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1 hour, and the holding time is 1.5 hours. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of ethylene glycol monovinyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1.8:0.15:0.1:0.008:0.08.

[0072] (2) Preparation of modified nano silica: Nano silica with an average particle size of 20 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and when the temperature was raised to 80 °C, diethylenetriaminepropyltriethoxysilane was added and the reaction was kept at the temperature for 4 h. Then p-toluenesulfonic acid was added, the temperature was raised to 150 °C, 2,2-bis(hydroxymethyl)propionic acid was added, and the reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, diethylenetriaminepropyltriethoxysilane, 2,2-bis(hydroxymethyl)propionic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0073] (3) Preparation of high-performance grinding aid: Add 30% by weight of 2-hydroxymethyl-1,3-propanediol and 15% by weight of N-(3-aminopropyl)diethanolamine to a mixing tank, stir for 30 min, add 10% by weight of modified nano-silica, continue stirring for 30 min, and finally add 45% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-7 for ultrafine composite mineral admixture.

[0074] Example 8

[0075] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0076] (1) Preparation of polyamine carboxylic acid polymers:

[0077] 1) Same as Example 4.

[0078] 2) In another reactor, add 4-hydroxybutyl polyoxyethylene ether with a relative molecular weight of 800 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 2 hours, and the holding time is 1 hour. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of 4-hydroxybutyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:1.8:0.2:0.12:0.01:0.1.

[0079] (2) Preparation of modified nano silica: Nano silica with an average particle size of 30 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and when the temperature was raised to 80 °C, diethylaminomethyltriethoxysilane was added and the reaction was kept at the temperature for 4 h. Then p-toluenesulfonic acid was added, the temperature was raised to 150 °C, 2,2-dihydroxymethylbutyric acid was added, and the reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, diethylaminomethyltriethoxysilane, 2,2-dihydroxymethylbutyric acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0080] (3) Preparation of high-performance grinding aid: Add 25% by weight of 2-hydroxymethyl-2-methyl-1,3-propanediol and 20% by weight of N-acetylethanolamine to a mixing tank, stir for 30 min, add 5% by weight of modified nano-silica, continue stirring for 30 min, and finally add 50% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-8 for ultrafine composite mineral admixture.

[0081] Example 9

[0082] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0083] (1) Preparation of polyamine carboxylic acid polymers:

[0084] 1) Same as Example 1.

[0085] 2) In another reactor, add methyl allyl polyoxyethylene ether with a relative molecular weight of 600 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1 hour, and the holding time is 1.5 hours. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of methyl allyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:2.1:0.15:0.15:0.015:0.12.

[0086] (2) Preparation of modified nano silica: Nano silica with an average particle size of 50 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and 3-aminopropyltrimethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, then p-toluenesulfonic acid was added, the temperature was raised to 150 °C, 2,2-bis(hydroxymethyl)propionic acid was added, and the reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, 3-aminopropyltrimethoxysilane, 2,2-bis(hydroxymethyl)propionic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0087] (3) Preparation of high-performance grinding aid: Add 30% by weight of aminobutanetriol and 15% by weight of diethanol monoisopropanolamine to the mixing tank, stir for 30 min, add 15% by weight of modified nano silica, continue stirring for 30 min, and finally add 40% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-9 for ultrafine composite mineral admixture.

[0088] Example 10

[0089] The preparation method of the high-performance grinding aid for ultrafine composite mineral admixtures provided in this embodiment is as follows:

[0090] (1) Preparation of polyamine carboxylic acid polymers:

[0091] 1) Same as Example 2.

[0092] 2) In another reactor, add 4-hydroxybutyl polyoxyethylene ether with a relative molecular weight of 800 and deionized water. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1.5 h, and the holding time is 1 h. After the holding time is completed, spray dry to obtain a powdered polyamine carboxylic acid polymer. The molar ratio of 4-hydroxybutyl polyoxyethylene ether, acrylic acid, maleic polyamine, hydrogen peroxide, ascorbic acid and mercaptopropionic acid is 1:2.5:0.2:0.18:0.02:0.15.

[0093] (2) Preparation of modified nano silica: Nano silica with an average particle size of 80 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and 3-aminopropyltriethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, and then p-toluenesulfonic acid was added. The temperature was raised to 150 °C, and (R)-3-amino-2-(hydroxymethyl)propionic acid was added. The reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of nano silica, 3-aminopropyltriethoxysilane, (R)-3-amino-2-(hydroxymethyl)propionic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0094] (3) Preparation of high-performance grinding aid: Add 20% by weight of 1,3-bis(hydroxymethyl)urea and 25% by weight of N-(hydroxymethyl)ethanolamine to a mixing tank, stir for 30 min, add 10% by weight of modified nano-silica, continue stirring for 30 min, and finally add 45% by weight of polyamine carboxylic acid polymer and continue stirring for 1 h to obtain high-performance grinding aid ZM-10 for ultrafine composite mineral admixture.

[0095] Comparative Example 1

[0096] Commercially available triethanolamine (TEA), Shanghai Aladdin Biochemical Technology Co., Ltd.

[0097] Comparative Example 2

[0098] Commercially available ethylene glycol (EG), Shanghai Aladdin Biochemical Technology Co., Ltd.

[0099] Comparative Example 3

[0100] Commercially available composite grinding aid FZ, Sika (Jiangsu) Building Materials Co., Ltd.

[0101] Comparative Example 4

[0102] Maleic polyamine was not added during the preparation of the polyamine carboxylic acid polymer, and the rest was the same as in Example 1, to obtain grinding aid DM-1.

[0103] Comparative Example 5

[0104] Maleic polyamine was not added during the preparation of the polyamine carboxylic acid polymer, and the rest was the same as in Example 2, to obtain grinding aid DM-2.

[0105] Comparative Example 6

[0106] The high-performance grinding aid was prepared by replacing the modified nano-silica with unmodified nano-silica, and the rest was the same as in Example 1, to obtain grinding aid DM-3.

[0107] Comparative Example 7

[0108] The preparation method of the grinding aid provided in this comparative example is as follows:

[0109] (1) Preparation of polyamine carboxylic acid polymer: Same as in Example 1.

[0110] (2) Preparation of modified nano silica: Nano silica with an average particle size of 20 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and γ-glycidyl etheroxypropyltrimethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at this temperature for 4 h, and then p-toluenesulfonic acid was added. The temperature was raised to 150 °C, tartaric acid was added, and the reaction was kept at this temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of modified nano silica, γ-glycidyl etheroxypropyltrimethoxysilane, tartaric acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0111] (3) Preparation of high-performance grinding aid: Same as in Example 1, grinding aid DM-4 was obtained.

[0112] Comparative Example 8

[0113] The preparation method of the grinding aid provided in this comparative example is as follows:

[0114] (1) Preparation of polyamine carboxylic acid polymer: Same as in Example 2.

[0115] (2) Preparation of modified nano silica: Nano silica with an average particle size of 20 nm and xylene were added to the reaction vessel, stirred and nitrogen gas was introduced, and γ-glycidyl etheroxypropyltriethoxysilane was added when the temperature was raised to 80 °C. The reaction was kept at the temperature for 4 h, and then p-toluenesulfonic acid was added. The temperature was raised to 150 °C, malic acid was added, and the reaction was kept at the temperature for another 2 h. After the reaction was completed, the temperature was cooled to room temperature, and finally centrifuged and dried to obtain modified nano silica. The molar ratio of modified nano silica, γ-glycidyl etheroxypropyltriethoxysilane, malic acid and p-toluenesulfonic acid was 7:3:3:0.015.

[0116] (3) Preparation of high-performance grinding aid: Same as in Example 2, grinding aid DM-5 was obtained.

[0117] Implementation effect verification

[0118] The ultrafine composite mineral admixtures prepared in Examples 1-10 were compared with commercially available triethanolamine, ethylene glycol, composite grinding aids, and grinding aids prepared in Comparative Examples 4 to 8 using high-performance grinding aids. The raw materials used in the tests were steel slag, rice husk ash, red mud, carbide slag, pyrite slag, nickel slag, and lead-zinc tailings slag. The grinding aid dosage was 0.05% of the total mass of the raw materials. The composite mineral admixtures were prepared by grinding using a ball mill. The specific surface area under different grinding times and the time required to grind to different specific surface areas were tested. The specific test results are shown in Table 1.

[0119] Table 1. Experimental Results

[0120]

[0121] As shown in Table 1, compared with Comparative Examples 1-3, the specific surface area of ​​Examples 1-10 of the present invention increased by 10.4-45.8%, 10.4-35.8%, and 10.9-36.3% respectively when the grinding time was 30 min, 40 min, and 50 min, and the specific surface area increased further when the grinding time was 600 m². 2 / kg, 800m 2 / kg and 1000m 2 The grinding time required to grind / kg was reduced by 4-10 min, 9-24 min, and 16-46 min, respectively, indicating that the high-performance grinding aids of Examples 1-10, compared with the grinding aids of Comparative Examples 1-3, not only significantly increased the specific surface area of ​​the admixture under the same grinding time, but also greatly reduced the grinding time required to achieve the same specific surface area through ultrafine grinding; at the same time, for every 200 m² increase in specific surface area... 2 / kg, the increase in grinding time required for Examples 1-10 is much lower than that for Comparative Examples 1-3. Therefore, compared with Comparative Examples 1-3, the high-performance grinding aids prepared in Examples 1-10 of this invention not only have better grinding aid effects and higher grinding efficiency, but also more stable grinding performance.

[0122] Furthermore, compared with Example 1, Comparative Examples 4, 6, and 7 show that the introduction of maleic polyamine into the polyamine carboxylic acid polymer, the modification with nano-silica, and the use of silane modifiers and branching modifiers increased the specific surface area of ​​the admixture by 5.3-11.3%, 6.5-8.9%, and 6.7-9.6% respectively after milling for 30 min, 40 min, and 50 min. Moreover, the specific surface area increased to 600 m² / s, respectively. 2 / kg, 800m 2 / kg and 1000m 2 The time required to weigh / kg was reduced by 1-2 min, 6-7 min, and 9-10 min, respectively.

[0123] Finally, comparing Examples 5 and 8 with Example 2, it can be seen that the introduction of maleic polyamine into the polyamine carboxylic acid polymer and the use of silane modifiers and branching modifiers in the modified nano-silica increased the specific surface area of ​​the admixture by 6.9-10.9%, 7.7-10.5%, and 7.8-10.2% respectively after milling for 30 min, 40 min, and 50 min. Furthermore, when milled to a specific surface area of ​​600 m², the admixtures showed significant increases. 2 / kg, 800m 2 / kg and 1000m 2 The time required to weigh / kg was reduced by 2-3 min, 6-8 min, and 10-12 min, respectively.

[0124] In summary, the high-performance grinding aids prepared in Examples 1-10 of this invention not only have better grinding aid effects and higher grinding efficiency, but also more stable grinding performance.

[0125] It is understood that the present invention has been described through some embodiments, and those skilled in the art will recognize that various changes or equivalent substitutions can be made to these features and embodiments without departing from the spirit and scope of the invention. Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. It can be applied to various fields suitable for the present invention, and other modifications can be easily implemented by those skilled in the art. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and embodiments shown and described herein.

Claims

1. A high-performance grinding aid for ultrafine composite mineral admixtures, characterized in that, It includes the following components by weight percentage: 35-50% polyamine carboxylic acid polymer, 5-15% modified nano-silica, 15-30% polyol derivatives, and 15-30% alkanolamine derivatives; The polyamine carboxylic acid polymer is prepared according to the following steps: 1) Add organic polyamine to the reactor, stir and purge with nitrogen, then add maleic anhydride, seal the reactor opening, heat to 50°C and start heat preservation, and control the cooling water to ensure that the temperature inside the reactor is between 55-70°C for 1 hour. Finally, cool down to below 45°C, turn off the nitrogen and cooling water to obtain maleic polyamine monomer for later use. 2) Add polyether macromonomer and deionized water to another reactor. After the mixture is completely dissolved by stirring at room temperature, add hydrogen peroxide. Then, simultaneously add a mixed solution of acrylic acid, maleic polyamine monomer and deionized water, as well as a mixed solution of ascorbic acid, mercaptopropionic acid and deionized water. The addition time is 1-2 hours, and the holding time is 1-1.5 hours. After the holding time is completed, spray dry to obtain powdered polyamine carboxylic acid polymer. The modified nano-silica is prepared by the following steps: nano-silica and xylene are added to a reaction vessel, stirred and nitrogen gas is introduced, and when the temperature is raised to 80°C, a silane modifier is added and the reaction is maintained for 4 hours. Then, p-toluenesulfonic acid is added, the temperature is raised to 150°C, a branching modifier is added, and the reaction is maintained for another 2 hours. After the reaction is completed, the temperature is cooled to room temperature, and finally, centrifugation and drying are performed to obtain the modified nano-silica. The polyol derivative is one or more of 2-hydroxymethyl-1,3-propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-di(2-hydroxyethyl)amino-2-hydroxymethyl-1,3-propanediol, aminobutanetriol, and 2,2-dihydroxymethylbutanol. The alkanolamine derivative is one or more selected from N-(hydroxymethyl)ethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-nitrosodiethanolamine, N-(3-aminopropyl)diethanolamine, N-acetylethanolamine, and diethanolmonoisopropanolamine. The silane modifier is one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, diethylenetriaminopropyltriethoxysilane, and diethylaminomethyltriethoxysilane; the branching modifier is one or more of 2,2-bis(hydroxymethyl)propionic acid, 2,2-dihydroxymethylbutyric acid, and (R)-3-amino-2-(hydroxymethyl)propionic acid.

2. The high-performance grinding aid for ultrafine composite mineral admixtures as described in claim 1, characterized in that, The organic polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; the polyether macromonomer is one or more of methyl allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, ethylene glycol monovinyl polyoxyethylene ether, and 4-hydroxybutyl polyoxyethylene ether with relative molecular masses of 400, 600, 800, 1000, and 1200.

3. The high-performance grinding aid for ultrafine composite mineral admixtures as described in claim 1, characterized in that, The molar ratio of maleic anhydride to organic polyamine is 1:1.05; the molar ratio of polyether macromonomer, acrylic acid, maleic polyamine monomer, hydrogen peroxide, ascorbic acid, and mercaptopropionic acid is 1:(1.0-2.5):(0.1-0.2):(0.04-0.18):(0.005-0.02):(0.03-0.15).

4. The high-performance grinding aid for ultrafine composite mineral admixtures as described in claim 1, characterized in that, The nano-silica is one or more of the following: purity > 99.5%, hydroxyl content > 45%, and average particle size of 15nm, 20nm, 30nm, 50nm, and 80nm.

5. The high-performance grinding aid for ultrafine composite mineral admixtures as described in claim 1, characterized in that, The molar ratio of the nano-silica, silane modifier, branching modifier, and p-toluenesulfonic acid is 7:3:3:0.

015.

6. The method for preparing the high-performance grinding aid for ultrafine composite mineral admixtures as described in any one of claims 1 to 5, characterized in that, The following steps are followed to obtain the high-performance grinding aid for ultrafine composite mineral admixtures: add polyol derivatives and alkanolamine derivatives to a mixing tank, stir for 30 minutes, add modified nano-silica, continue stirring for 30 minutes, and finally add polyamine carboxylic acid polymer and continue stirring for 1 hour.

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