CN112830710A - Coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent and preparation method thereof - Google Patents
Coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent and preparation method thereof Download PDFInfo
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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
Abstract
The invention discloses a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent and a preparation method thereof, wherein the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent comprises 1-10% by mass of a dispersing agent, 0.05-1% by mass of a coupling agent, 5-30% by mass of hydrated CSH synthesized by a soluble calcium source and a soluble silicon source through solution precipitation, and the balance of deionized water, wherein the molar ratio of calcium to silicon is 0.5-2.0. The preparation method comprises the following steps: and (3) taking the aqueous solution of the polycarboxylic acid dispersing agent and the silane coupling agent as a base material, and simultaneously dropwise adding the soluble calcium source aqueous solution and the soluble silicon source aqueous solution into the base material to obtain the nano calcium silicate hydrate crystal nucleus early strength agent. The coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent can rapidly promote cement hydration, shorten the setting time, greatly improve the hourly strength of concrete and slightly improve the medium and later strength. Is suitable for different rubber material systems and different temperature conditions.
Description
Technical Field
The invention relates to a concrete early strength agent, in particular to a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent and a preparation method thereof.
Background
With the continuous development of infrastructure construction, natural resources are in increasing shortage, particularly, concrete raw materials are about to be exhausted, and in order to improve the recycling rate of concrete structures, prefabricated parts and prefabricated buildings are continuously banned from on-site concrete pouring. The prefabricated parts and the assembled parts have the condition of short supply and short demand, so that new requirements are provided for the prefabricated parts, and higher early strength is required, so that the prefabrication period is shortened, the turnover of a mold is improved, and the energy consumption for maintenance is reduced.
The hydrated nano calcium silicate crystal nucleus is a pre-hydrated cement hydration product, is added into a concrete mixture, can provide an additional nucleation site in the early stage of cement hydration, effectively reduces the supersaturated crystallization concentration of the hydration product, greatly accelerates the cement hydration process, and has the advantages of obvious economic, environment-friendly and early-strength effects and the like compared with the traditional early strength agent. The Chinese patent publication date is 6 and 9 in 2020, publication number is CN111253107A, and the name is 'an alcohol amine modified calcium silicate hydrate nano crystal nucleus early strength agent and a preparation method thereof', and discloses an alcohol amine modified calcium silicate hydrate nano crystal nucleus early strength agent which comprises soluble calcium salt and soluble silicon salt, a polycarboxylic acid high-efficiency water reducing agent, a soluble alcohol amine organic matter and soluble aluminum salt. The Chinese patent publication date is 2019, 10 and 15, and the publication number is CN110330257A, and the name is C-S-H gel nanocrystal core early strength agent and a preparation method and application thereof, and the C-S-H gel nanocrystal core early strength agent is disclosed, wherein the preparation method comprises the steps of carrying out ball milling on 10-20 parts of tricalcium silicate, 0.5-1 part of ion accelerator, 0.1-0.3 part of surface modifier, 0.1-0.5 part of dispersion stabilizer and 78.5-89.2 parts of water, and the prepared C-S-H gel nanocrystal core early strength agent can improve the pore structure and induce nucleation to achieve the aim of early strength. The publication date is 2017, 11 and 17, publication number is CN107352836A, and name "super early strength type concrete admixture super strong crystal nucleus and preparation method thereof" discloses a preparation method of super early strength concrete admixture super strong crystal nucleus: stabilizer, dispersant, calcium silicate, triethanolamine, calcium nitrate and water are added into the priming water solution in a certain proportion, so as to obtain the super-strong crystal nucleus early strength agent of the super-early strength concrete admixture, and the patent does not describe the stability and the specific use effect of the crystal nucleus. The technology utilizes the ion complexation of the dispersing agent on the surface of the C-S-H crystal nucleus to be adsorbed on the surface of the C-S-H crystal nucleus, so that the nano dispersion of the C-S-H crystal nucleus is realized, but the charge balance is easy to break, so that the particle size of the CSH crystal nucleus is large, the effective surface area is reduced, and the early strength effect is not obvious when the doping amount is low.
According to the method, by adopting a coupling agent, the inorganic compound calcium silicate hydrate and the organic dispersing agent are chemically bonded, one end of the coupling agent reacts with the calcium silicate hydrate, and the other end of the coupling agent reacts with the dispersing agent, so that an inorganic/organic interface combination mode is improved, the dispersion degree of C-S-H crystal nuclei is greatly improved, the growth of the C-S-H crystal nuclei is effectively inhibited, more effective specific surface areas can be provided at a lower mixing amount, and a better early strength effect is obtained.
Disclosure of Invention
1. The technical problem to be solved is as follows:
in the prior art, the dispersant is adsorbed on the surface of the C-S-H crystal nucleus by utilizing the ion complexing action of the dispersant on the surface of the C-S-H crystal nucleus, so that the nano dispersion of the C-S-H crystal nucleus is realized, but the charge balance is easy to break, so that the particle size of the CSH crystal nucleus is large, the effective surface area is reduced, and the early strength effect is not obvious when the doping amount is low.
2. The technical scheme is as follows:
in order to solve the problems, the invention provides a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent, which comprises 1-10% of a dispersing agent by mass, 0.05-1% of a coupling agent by mass, 5-30% of hydrated CSH synthesized by a soluble calcium source and a soluble silicon source through solution precipitation and the balance of deionized water, wherein the molar ratio of calcium to silicon is 0.5-2.0.
The invention also provides a preparation method of the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent
3. Has the advantages that:
the invention modifies the surface of the nano calcium silicate hydrate by introducing the coupling agent, improves the hydrophilicity of the nano calcium silicate hydrate, is beneficial to the stability of a colloid dispersion system, realizes the perfect combination of inorganic nano calcium silicate hydrate and an organic polycarboxylic acid dispersant, is more beneficial to the performance exertion of the dispersant, provides higher electrostatic repulsion and steric hindrance, and inhibits the nano calcium silicate hydrate. The obtained coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent can obviously improve the early strength of concrete and has certain improvement on the middle and later strength. The compactness of the hardened concrete can be improved, and harmful holes are reduced, so that the durability of the concrete is improved, and the long-term social and economic benefits are achieved; can be used as superfine aggregate, optimizes the grain composition of concrete mixture and improves the workability of the concrete mixture.
According to the method, by adopting a coupling agent, the inorganic compound calcium silicate hydrate and the organic dispersing agent are chemically bonded, one end of the coupling agent reacts with the calcium silicate hydrate, and the other end of the coupling agent reacts with the dispersing agent, so that an inorganic/organic interface combination mode is improved, the dispersion degree of C-S-H crystal nuclei is greatly improved, the growth of the C-S-H crystal nuclei is effectively inhibited, more effective specific surface areas can be provided at a lower mixing amount, and a better early strength effect is obtained.
Detailed Description
The present invention will be described in detail by examples.
The invention provides a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent, which comprises 1-10% of a dispersing agent by mass, 0.05-1% of a coupling agent by mass, 5-30% of hydrated CSH synthesized by a soluble calcium source and a soluble silicon source through solution precipitation and the balance of deionized water, wherein the molar ratio of calcium to silicon is 0.5-2.0.
The dispersing agent is a polycarboxylic acid structure with the molecular weight of 10000-100000, and the structural formula is as follows:
The coupling agent is 3-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, gamma-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, N-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, diethylaminomethyltriethoxysilane, anilinomethyltriethoxysilane, dichloromethyltriethoxysilane, or mixtures thereof, Dichloromethyltriethoxysilane, bis (gamma-triethoxysilylpropyl) -tetrasulfide, phenyltrimethoxysilane, phenyltriethoxysilane, isopropyltris (dioctylphosphato) titanate, isopropyldioleaato (diisooctylphosphoryloxy) titanate, monoalkoxyunsaturated fatty acid titanate, chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine, bis (dioctyloxypyrophosphate) ethylene titanate, vegetable acid type monoalkoxy titanate, pyrophosphato type monoalkoxy titanate, chelate phosphate titanium coupling agent quaternary ammonium salt, tetraisopropylbis (dioctylphosphato) titanate, phosphate acyloxyisooctanol aluminate, triisopropyl borate, isopropyldioctadecyl borate, di (octadecyl) phosphate, di (octadecyl phosphate) borate, di (octadecyl phosphate) borate, tri (octadecyl, One or more of isopropyl-dodecyl-bis (borate), triethanolamine borate and tert-butyl-diethanolamide borate.
The soluble calcium source is one or more of calcium nitrate tetrahydrate, calcium formate, calcium acetate, calcium chloride, calcium gluconate, calcium hydrogen phosphate and calcium lactate.
The soluble silicon source is one or a mixture of more of methyl orthosilicate, ethyl orthosilicate, sodium metasilicate pentahydrate, potassium silicate, sodium metasilicate nonahydrate and lithium silicate.
The preparation method of the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent comprises the following steps: step S01: adding a dispersing agent and a coupling agent into a container, then supplementing ionized water to half of the mass of the prepared early strength agent, and placing the dispersing agent, the coupling agent and the ionized water into a water bath kettle to be stirred to prepare a base material; step S02: simultaneously dripping a soluble calcium source aqueous solution and a soluble silicon source aqueous solution into the base material prepared in the step S01, and preserving heat after finishing dripping; step S03: and supplementing the ionized water into the base material until the mass of the early strength agent to be prepared is reached, so as to obtain the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent.
In step S01, the stirring speed is 300 to 1600 rpm.
In step S01, the temperature of the water bath is 25-85 ℃.
In step S02, the soluble calcium source aqueous solution and the soluble silicon source aqueous solution are added dropwise for 3 to 10 hours.
In step S02, the heat preservation time is 1-3 h.
The following examples are all prepared by 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent.
Example 1
The preparation method comprises the following steps of preparing 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent:
(1) placing 25 parts of polycarboxylic acid dispersant and 2.5 parts of 3-aminopropyltrimethoxysilane coupling agent into a 3-neck flask with a stirring device, then supplementing deionized water to 500 parts, installing the three-neck flask with the stirring device, placing the three-neck flask into a water bath kettle, controlling the water bath temperature at 35 ℃, and controlling the stirring speed at 800 rpm;
(2) preparing 100 parts of aqueous solution with the mass concentration of 20% by 20 parts of calcium nitrate tetrahydrate, and preparing 150 parts of aqueous solution with the mass concentration of 20% by 30 parts of sodium metasilicate pentahydrate;
(3) dripping the calcium nitrate tetrahydrate aqueous solution and the sodium metasilicate pentahydrate aqueous solution obtained in the step (2) into the base material obtained in the step (1) at the same time, wherein the dripping time is 5 hours, the heat preservation time is 1 hour, and the dripping temperature and the heat preservation temperature are both controlled to be 35 ℃ so as to obtain a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution;
(4) and (4) supplementing 250 parts of deionized water to the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution obtained in the step (3) to obtain 1000 parts of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent in parts by weight.
Example 2
The preparation method comprises the following steps of preparing 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent:
(1) placing 25 parts of polycarboxylic acid dispersant and 2.5 parts of 3-glycidyl ether oxypropyltrimethoxysilane coupling agent into a 3-neck flask with a stirring device, then supplementing deionized water to 500 parts, installing the three-neck flask into the stirring device, placing the three-neck flask into a water bath kettle, controlling the water bath temperature at 45 ℃ and the stirring rate at 800 rpm;
(2) preparing 100 parts of 20% aqueous solution of calcium acetate and 150 parts of 20% aqueous solution of sodium metasilicate pentahydrate, wherein the 100 parts of the aqueous solution are prepared from 20 parts of calcium acetate;
(3) simultaneously dripping the calcium acetate aqueous solution and the sodium metasilicate pentahydrate aqueous solution obtained in the step (2) into the base material obtained in the step (1), wherein the dripping time is 4 hours, the heat preservation time is 2 hours, and the dripping temperature and the heat preservation temperature are both controlled to be 45 ℃ so as to obtain a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution;
(4) and (4) supplementing 250 parts of deionized water to the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution obtained in the step (3) to obtain 1000 parts of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent in parts by weight.
Example 3
The preparation method comprises the following steps of preparing 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent:
(1) putting 35 parts of polycarboxylic acid dispersant and 5.5 parts of vinyl triethoxysilane coupling agent into a 3-neck flask with a stirring device, then supplementing deionized water to 500 parts, putting the three-neck flask into the stirring device, putting the three-neck flask into a water bath kettle, controlling the water bath temperature at 45 ℃ and the stirring speed at 800 rpm;
(2) preparing 120 parts of 25 mass percent aqueous solution from 30 parts of calcium hydrophosphate, and preparing 150 parts of 20 mass percent aqueous solution from 30 parts of ethyl orthosilicate;
(3) simultaneously dripping the calcium acetate aqueous solution and the sodium metasilicate pentahydrate aqueous solution obtained in the step (2) into the base material obtained in the step (1), wherein the dripping time is 4 hours, the heat preservation time is 2 hours, and the dripping temperature and the heat preservation temperature are both controlled to be 45 ℃ so as to obtain a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution;
(4) and (4) supplementing 230 parts of deionized water to the coupling agent modified calcium silicate nano-hydrate crystal nucleus early strength agent concentrated solution obtained in the step (3) to obtain 1000 parts of coupling agent modified calcium silicate nano-hydrate crystal nucleus early strength agent in parts by weight.
Example 4
The preparation method comprises the following steps of preparing 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent:
(1) placing 15 parts of polycarboxylic acid dispersant and 5.2 parts of vinyl triethoxysilane coupling agent in a 3-neck flask with a stirring device, then supplementing deionized water to 500 parts, installing the three-neck flask in the stirring device, placing the three-neck flask in a water bath kettle, controlling the water bath temperature at 45 ℃ and the stirring speed at 800 rpm;
(2) preparing 120 parts of 25 mass% aqueous solution from 30 parts of calcium hydrophosphate and 100 parts of 20 mass% aqueous solution from 20 parts of methyl orthosilicate;
(3) simultaneously dripping the calcium acetate aqueous solution and the sodium metasilicate pentahydrate aqueous solution obtained in the step (2) into the base material obtained in the step (1), keeping the dripping time at 5h and the heat preservation time at 2h, and controlling the dripping temperature and the heat preservation temperature to be 45 ℃ to obtain a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution;
(4) and (4) adding 280 parts of deionized water into the coupling agent modified calcium silicate nano-hydrate crystal nucleus early strength agent concentrated solution obtained in the step (3) to obtain 1000 parts of coupling agent modified calcium silicate nano-hydrate crystal nucleus early strength agent in parts by weight.
Example 5
The preparation method comprises the following steps of preparing 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent:
(1) placing 35 parts of polycarboxylic acid dispersant and 6.3 parts of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate coupling agent into a 3-neck flask with a stirring device, then supplementing deionized water to 500 parts, installing the three-neck flask into the stirring device, placing the three-neck flask into a water bath kettle, controlling the water bath temperature at 65 ℃ and the stirring rate at 800 rpm;
(2) preparing 150 parts of aqueous solution with the mass concentration of 20% by 30 parts of calcium nitrate tetrahydrate, and preparing 100 parts of aqueous solution with the mass concentration of 20% by 20 parts of lithium silicate;
(3) simultaneously dripping the calcium acetate aqueous solution and the sodium metasilicate pentahydrate aqueous solution obtained in the step (2) into the base material obtained in the step (1), keeping the dripping time at 5h and the heat preservation time at 1h, and controlling the dripping temperature and the heat preservation temperature to be 65 ℃ to obtain a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution;
(4) and (4) supplementing 250 parts of deionized water to the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution obtained in the step (3) to obtain 1000 parts of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent in parts by weight.
Example 6
The preparation method comprises the following steps of preparing 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent:
(1) placing 25 parts of polycarboxylic acid dispersant and 2.9 parts of chelate coupling agent of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine in a 3-neck flask with a stirring device, then supplementing deionized water to 500 parts, mounting the three-neck flask on the stirring device, placing the three-neck flask in a water bath kettle, controlling the water bath temperature at 65 ℃ and the stirring rate at 800 rpm;
(2) preparing 150 parts of aqueous solution with the mass concentration of 20% by 30 parts of calcium nitrate tetrahydrate, and preparing 150 parts of aqueous solution with the mass concentration of 20% by 30 parts of sodium metasilicate nonahydrate;
(3) simultaneously dripping the calcium acetate aqueous solution and the sodium metasilicate pentahydrate aqueous solution obtained in the step (2) into the base material obtained in the step (1), wherein the dripping time is 5 hours, the heat preservation time is 1.5 hours, and the dripping temperature and the heat preservation temperature are both controlled to be 65 ℃ to obtain a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution;
(4) and (4) supplementing 200 parts of deionized water to the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution obtained in the step (3) to obtain 1000 parts of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent in parts by weight.
Example 7
The preparation method comprises the following steps of preparing 1000 parts by weight of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent:
(1) 40 parts of polycarboxylic acid dispersant and 7.8 parts of isopropyl-di (dodecyl) borate coupling agent are placed in a 3-neck flask with a stirring device, then deionized water is replenished to 500 parts, a three-neck flask is installed on the stirring device and placed in a water bath kettle, the water bath temperature is controlled at 55 ℃, and the stirring speed is controlled at 1200 rpm;
(2) preparing 200 parts of aqueous solution with the mass concentration of 20% by 40 parts of calcium nitrate tetrahydrate, and preparing 150 parts of aqueous solution with the mass concentration of 20% by 30 parts of sodium metasilicate nonahydrate;
(3) simultaneously dripping the calcium acetate aqueous solution and the sodium metasilicate pentahydrate aqueous solution obtained in the step (2) into the base material obtained in the step (1), wherein the dripping time is 5 hours, the heat preservation time is 1.5 hours, and the dripping temperature and the heat preservation temperature are both controlled to be 55 ℃ so as to obtain a coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution;
(4) and (4) supplementing 150 parts of deionized water to the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent concentrated solution obtained in the step (3) to obtain 1000 parts of coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent in parts by weight.
Test examples concrete Performance test
The control group 1 adopts a CSH crystal nucleus early strength agent sold in a certain manufacturer, the control group 2 is a blank group without any early strength additive, and the doping amount of the crystal nucleus type early strength agent sample is 0.5 percent of the mass of the cement. The test refers to GB8076-2012 concrete admixture to carry out concrete workability and strength detection.
The test results are shown in Table 1.
TABLE 1 concrete test results
As can be seen from Table 1, the crystal nucleus early strength agent prepared by the invention has certain water reducing performance, can improve the workability of concrete, has excellent early strength effect, obviously improves the early strength, and also improves the 28 strength to a certain extent.
According to the invention, by adopting a coupling agent method, the inorganic compound calcium silicate hydrate and the organic dispersing agent are chemically bonded, one end of the coupling agent reacts with the calcium silicate hydrate, and the other end of the coupling agent reacts with the dispersing agent, so that an inorganic/organic interface combination mode is improved, the dispersion degree of C-S-H crystal nuclei is greatly improved, the growth of the C-S-H crystal nuclei is effectively inhibited, more effective specific surface area can be provided at a lower doping amount, and a better early strength effect is obtained.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A coupling agent modified nanometer calcium silicate hydrate crystal nucleus early strength agent is characterized in that: the calcium-silicon composite material comprises 1-10% by mass of a dispersing agent, 0.05-1% by mass of a coupling agent, 5-30% by mass of hydrated CSH synthesized by a soluble calcium source and a soluble silicon source through solution precipitation and the balance of deionized water, wherein the molar ratio of calcium to silicon is 0.5-2.0.
2. The coupling agent modified calcium nano-silicate hydrate crystal nucleus early strength agent as claimed in claim 1, wherein: the dispersing agent is a polycarboxylic acid structure with the molecular weight of 10000-100000, and the structural formula is as follows:
wherein a is an integer of 30 to 100, b is an integer of 0 to 30, and c is an integer of 10 to 30; r1、R3、R5Each represents H atom or CH3，R2Represents COOH, R4Represents CONH2、SO3Na、CONHC(CH3)2CH2SO3Na、COO(CH2)3Si(OCH3)3、COO(CH2)3Si(OC2H6)3、COO(CH2)2N(CH3)3One or more of Cl and benzene ring, R6Represents polyoxyethylene ether with the molecular weight of 1000-5000.
3. The coupling agent modified calcium nano-silicate hydrate crystal nucleus early strength agent as claimed in claim 1, wherein: the coupling agent is 3-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, gamma-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, N-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, diethylaminomethyltriethoxysilane, anilinomethyltriethoxysilane, dichloromethyltriethoxysilane, or mixtures thereof, Dichloromethyltriethoxysilane, bis (gamma-triethoxysilylpropyl) -tetrasulfide, phenyltrimethoxysilane, phenyltriethoxysilane, isopropyltris (dioctylphosphato) titanate, isopropyldioleaato (diisooctylphosphoryloxy) titanate, monoalkoxyunsaturated fatty acid titanate, chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine, bis (dioctyloxypyrophosphate) ethylene titanate, vegetable acid type monoalkoxy titanate, pyrophosphato type monoalkoxy titanate, chelate phosphate titanium coupling agent quaternary ammonium salt, tetraisopropylbis (dioctylphosphato) titanate, phosphate acyloxyisooctanol aluminate, triisopropyl borate, isopropyldioctadecyl borate, di (octadecyl) phosphate, di (octadecyl phosphate) borate, di (octadecyl phosphate) borate, tri (octadecyl, One or more of isopropyl-dodecyl-bis (borate), triethanolamine borate and tert-butyl-diethanolamide borate.
4. The coupling agent modified calcium nano-silicate hydrate crystal nucleus early strength agent as claimed in claim 1, wherein: the soluble calcium source is one or more of calcium nitrate tetrahydrate, calcium formate, calcium acetate, calcium chloride, calcium gluconate, calcium hydrogen phosphate and calcium lactate.
5. The coupling agent modified calcium nano-silicate hydrate crystal nucleus early strength agent as claimed in claim 1, wherein: the soluble silicon source is one or a mixture of more of methyl orthosilicate, ethyl orthosilicate, sodium metasilicate pentahydrate, potassium silicate, sodium metasilicate nonahydrate and lithium silicate.
6. A method for preparing the coupling agent modified calcium nano-silicate hydrate crystal nucleus early strength agent as claimed in any one of claims 1 to 5, which comprises the following steps: step S01: adding a dispersing agent and a coupling agent into a container, then supplementing ionized water to half of the mass of the prepared early strength agent, and placing the dispersing agent, the coupling agent and the ionized water into a water bath kettle to be stirred to prepare a base material; step S02: simultaneously dripping a soluble calcium source aqueous solution and a soluble silicon source aqueous solution into the base material prepared in the step S01, and preserving heat after finishing dripping; step S03: and supplementing the ionized water into the base material until the mass of the early strength agent to be prepared is reached, so as to obtain the coupling agent modified nano calcium silicate hydrate crystal nucleus early strength agent.
7. The method of claim 6, wherein: in step S01, the stirring speed is 300 to 1600 rpm.
8. The method of claim 6, wherein; in step S01, the temperature of the water bath is 25-85 ℃.
9. The method of claim 6, wherein; in step S02, the soluble calcium source aqueous solution and the soluble silicon source aqueous solution are added dropwise for 3 to 10 hours.
10. The method of claim 6, wherein: in step S02, the heat preservation time is 1-3 h.
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| CN113929341A (en) * | 2021-10-29 | 2022-01-14 | 四川华西绿舍建材有限公司 | Nano crystal seed ultra-early strength agent suitable for low-temperature environment and preparation method thereof |
| CN114656191A (en) * | 2022-04-28 | 2022-06-24 | 江苏博拓新型建筑材料股份有限公司 | Method for preparing crystal nucleus early-strength polycarboxylate superplasticizer with long-term dispersibility |
| CN114835427A (en) * | 2022-05-25 | 2022-08-02 | 中国水利水电第十二工程局有限公司 | Preparation method of early strength agent for preparing low-temperature and large-water-cement-ratio concrete |
| CN115432956A (en) * | 2022-09-28 | 2022-12-06 | 艾思尔信息科技(上海)有限公司 | Cement retarding reinforcing agent and preparation method and device thereof |
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| CN114835427A (en) * | 2022-05-25 | 2022-08-02 | 中国水利水电第十二工程局有限公司 | Preparation method of early strength agent for preparing low-temperature and large-water-cement-ratio concrete |
| CN115432956A (en) * | 2022-09-28 | 2022-12-06 | 艾思尔信息科技(上海)有限公司 | Cement retarding reinforcing agent and preparation method and device thereof |
| CN115432956B (en) * | 2022-09-28 | 2024-01-12 | 艾思尔信息科技(上海)有限公司 | Cement retarding enhancer and preparation method and device thereof |
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Application publication date: 20210525 |