CN111377655B - Covalent bond type alkali-free accelerator and preparation method thereof - Google Patents
Covalent bond type alkali-free accelerator and preparation method thereof Download PDFInfo
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- CN111377655B CN111377655B CN201811636662.2A CN201811636662A CN111377655B CN 111377655 B CN111377655 B CN 111377655B CN 201811636662 A CN201811636662 A CN 201811636662A CN 111377655 B CN111377655 B CN 111377655B
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- covalent bond
- free accelerator
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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
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a covalent bond type alkali-free accelerator and a preparation method thereof. The alkali-free accelerator disclosed by the invention comprises the following components in percentage by mass: 40-50% of an inorganic component A, 5-10% of alcohol amine, 1-3% of organic acid, 12-15% of an organic component B, 0.25-0.35% of catechol and the balance of water, wherein the inorganic component A is prepared from 200-300 meshes of polyaluminium sulfate, nano gamma-alumina, a silane coupling agent solution and a 95wt% ethanol water solution in proportion; the organic component B is prepared from dimethyl diallyl ammonium chloride, acrylic acid and initiator water in proportion. The invention has long service life and good construction performance; the introduced organic components have higher charge density and proper molecular weight, and can be bonded and precipitated with calcium ions in cement, so that gypsum consumption is promoted, the hydration rate of C3A is increased, and the setting time of the product is shortened.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a covalent bond type alkali-free accelerator and a preparation method thereof.
Background
The accelerator is a concrete admixture which rapidly sets and hardens cement or concrete. The method has the main effects of increasing the primary spraying thickness of the sprayed concrete, shortening the interval between secondary spraying, and simultaneously improving the early strength of the concrete so as to provide support resistance in time, and is widely applied to the engineering of modern underground engineering, mine engineering, leakage stoppage, emergency rescue and the like at present.
The alkali-free accelerator has almost no influence on the later strength of concrete, and is the main development direction of the accelerator, and the alkali-free accelerator taking aluminum sulfate as a main component is a main research object of the accelerator due to the easily available raw material sources and simple preparation process.
The traditional aluminum sulfate alkali-free accelerator is modified by organic alcohol amine and inorganic salt. Patent CN10912563.1 discloses an organic-inorganic composite alkali-free accelerator and a preparation method thereof, wherein aluminum salt and alcohol amine are adopted to form a complex, and magnesium salt and the like are adopted to increase the complexing stability. Patent CN201711214589.5 discloses a novel alkali-free accelerator synthesized from organic and inorganic acids and a preparation method thereof, wherein citric acid and aluminum ions are adopted to form a stable complex, hydrofluoric acid is continuously introduced to increase the reaction conversion rate, and finally alcohol amine is introduced to improve the early strength of the product and the comprehensive performance of the product. In the case of the conventional aluminum sulfate-based alkali-free setting accelerator, in terms of hybrid nature and bonding form, organic and inorganic phases are combined by the interaction of hydrogen bonds and van der waals force, and the continuous brownian movement inevitably causes product delamination or precipitation along with the increase of the standing time, and the sale and use of the product are influenced.
Disclosure of Invention
The invention provides a covalent bond type alkali-free accelerator and a preparation method thereof, aiming at solving the defects of short service life and the like of the existing alkali-free accelerator.
Organic matters and inorganic components of the traditional aluminum sulfate alkali-free accelerator are mostly combined by weak interaction such as hydrogen bonds and hydrophilic-hydrophobic balance, and the continuous Brownian motion can increase the collision probability among particles, so that the product is layered or precipitated. Organic silicon is used as a bridge for connecting the inorganic component and the organic component, and an organic functional group is introduced to the inorganic component, so that the organic component and the inorganic component are connected by a chemical bond of a covalent bond, and the phenomenon of macroscopic phase separation of a product is prevented.
The covalent bond type alkali-free accelerator comprises the following components in percentage by mass:
the sum of the mass percentages of the components is 100 percent;
the inorganic component A comprises the following components in percentage by mass
The sum of the mass percentages of the components is 100 percent,
wherein the solvent in the silane coupling agent solution is ethanol, the mass concentration of the silane coupling agent in the solution is 1-3 wt%, and the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane;
the organic component B comprises the following components in percentage by mass:
the sum of the mass percentages of the components is 100 percent,
wherein the initiator is any one of ammonium persulfate, sodium persulfate and potassium persulfate.
The alcohol amine is diethanolamine or triethanolamine; the organic acid is lactic acid or oxalic acid.
The invention relates to a preparation method of a covalent bond type alkali-free accelerator, which comprises the following steps:
(1) adding 200-300 meshes of polyaluminium sulfate and nano gamma-alumina into 95wt% ethanol water solution, and then performing ultrasonic dispersion for 1h to obtain uniformly dispersed suspension; then adding the completely hydrolyzed silane coupling agent solution; stirring and reacting at 80 ℃ for 24h under the protection of nitrogen, then centrifugally separating, washing with ethanol for 3 times, and finally vacuum drying at 60 ℃ to obtain an inorganic component A;
(2) uniformly mixing dimethyl diallyl ammonium chloride, acrylic acid and water, and then adding an initiator to uniformly mix to obtain an organic component B;
(3) and (2) uniformly mixing the inorganic component A prepared in the step (1), alcohol amine, organic acid and water, heating to 60-80 ℃, then respectively adding the organic component B prepared in the step (2) and catechol, reacting for 2-6 h under heat preservation, and cooling to room temperature to obtain the covalent bond type alkali-free accelerator.
The covalent bond type alkali-free accelerator is used in the field of sprayed concrete, and the dosage of the covalent bond type alkali-free accelerator is 6-9wt% of the dosage of cement.
The invention has the beneficial effects that: the silane coupling agent is used as a bridge, organic functional groups are introduced to the inorganic component, and then covalent bonds are directly formed with the organic component, so that organic-inorganic hybrid compounding in the true sense is realized, the collision chance among inorganic particles is reduced, the organic chain can also prevent the inorganic component from being excessively aggregated, the phenomenon of layering or precipitation of the product is prevented, and the excellent product with long service life and good construction performance is obtained. In addition, the introduced organic components have higher charge density and proper molecular weight, can be bonded and precipitated with calcium ions in cement, further promote the consumption of gypsum, improve the hydration rate of C3A and shorten the setting time of the product.
Detailed Description
In order to enhance the understanding of the method, the method will be described in further detail with reference to the following examples, which are only used for explaining the method and do not limit the scope of the method.
In order to better understand the invention, the following examples are given for further illustration of the invention, but the invention is not limited to the scope of the examples.
Example 1
The preparation method of the covalent bond type alkali-free accelerator comprises the following steps:
(1) adding 4g of 200-300-mesh polyaluminium sulfate and 1g of nano gamma-alumina into 90g of 95wt% ethanol aqueous solution, and then performing ultrasonic dispersion for 1 hour to obtain uniformly dispersed suspension; then 5g of a 1 wt% ethanol solution of gamma-methacryloxypropyltrimethoxysilane which had been completely hydrolyzed was added; stirring and reacting at 80 ℃ for 24h under the protection of nitrogen, then centrifugally separating, washing with ethanol for 3 times, and finally vacuum drying at 60 ℃ to obtain the inorganic component A.
(2) 20g of dimethyldiallylammonium chloride, 25g of acrylic acid and 54.8g of water are mixed uniformly, and then 0.2g of ammonium persulfate is added and mixed uniformly to obtain the organic component B.
(3) Uniformly mixing 40g of inorganic component A, 5g of diethanolamine, 3g of oxalic acid and 39.75g of water, heating to 60 ℃, then respectively adding 12g of organic component B and 0.25g of catechol, carrying out heat preservation reaction for 6h, and cooling to room temperature to obtain the covalent bond type composite alkali-free accelerator.
Example 2
The preparation method of the covalent bond type alkali-free accelerator comprises the following steps:
(1) adding 4.9g of 200-300-mesh polyaluminium sulfate and 0.1g of nano gamma-alumina into 91g of 95wt% ethanol aqueous solution, and then performing ultrasonic dispersion for 1 hour to obtain uniformly dispersed suspension; then 4g of a 3wt% ethanol solution of gamma-methacryloxypropyltrimethoxysilane which had been completely hydrolyzed were added; stirring and reacting at 80 ℃ for 24h under the protection of nitrogen, then centrifugally separating, washing with ethanol for 3 times, and finally vacuum drying at 60 ℃ to obtain the inorganic component A.
(2) 25g of dimethyldiallylammonium chloride, 20g of acrylic acid and 53.8g of water are mixed uniformly, and then 1.2g of sodium persulfate is added and mixed uniformly to obtain an organic component B.
(3) Uniformly mixing 50g of inorganic component A, 10g of triethanolamine, 1g of lactic acid and 23.65g of water, heating to 80 ℃, then respectively adding 15g of organic component B and 0.35g of catechol, carrying out heat preservation reaction for 2h, and cooling to room temperature to obtain the covalent bond type composite alkali-free accelerator.
Example 3
The preparation method of the covalent bond type alkali-free accelerator comprises the following steps:
(1) adding 4g of 200-300-mesh polyaluminium sulfate and 1g of nano gamma-alumina into 90.5g of 95wt% ethanol aqueous solution, and then performing ultrasonic dispersion for 1 hour to obtain uniformly dispersed suspension; then 4.5g of 2 wt% of a completely hydrolyzed ethanol solution of gamma-methacryloxypropyltrimethoxysilane was added; stirring and reacting at 80 ℃ for 24h under the protection of nitrogen, then centrifugally separating, washing with ethanol for 3 times, and finally vacuum drying at 60 ℃ to obtain the inorganic component A.
(2) 22g of dimethyldiallylammonium chloride, 23g of acrylic acid and 54g of water are mixed uniformly, and then 1g of potassium persulfate is added and mixed uniformly to obtain an organic component B.
(3) Uniformly mixing 50g of inorganic component A, 10g of triethanolamine, 1g of lactic acid and 23.65g of water, heating to 80 ℃, then respectively adding 15g of organic component B and 0.35g of catechol, carrying out heat preservation reaction for 2h, and cooling to room temperature to obtain the covalent bond type composite alkali-free accelerator.
Example 4
The preparation method of the covalent bond type alkali-free accelerator comprises the following steps:
(1) adding 4.6g of 200-300-mesh polyaluminium sulfate and 0.4g of nano gamma-alumina into 90g of 95wt% ethanol aqueous solution, and then performing ultrasonic dispersion for 1 hour to obtain uniformly dispersed suspension; then 5g of 2 wt% of a completely hydrolyzed ethanol solution of gamma-methacryloxypropyltrimethoxysilane was added; stirring and reacting at 80 ℃ for 24h under the protection of nitrogen, then centrifugally separating, washing with ethanol for 3 times, and finally vacuum drying at 60 ℃ to obtain the inorganic component A.
(2) 21g of dimethyldiallylammonium chloride, 24g of acrylic acid and 54.2g of water are mixed uniformly, and then 0.8g of ammonium persulfate is added and mixed uniformly to obtain the organic component B.
(3) Uniformly mixing 45g of inorganic component A, 9g of diethanolamine, 2g of lactic acid and 30.7g of water, heating to 70 ℃, then respectively dripping 13g of organic component B and 0.3g of catechol, carrying out heat preservation reaction for 4h, and cooling to room temperature to obtain the covalent bond type composite alkali-free accelerator.
Comparative example 1
Heating 40g of polyaluminium sulfate, 10g of nano gamma-alumina, 10g of diethanolamine, 2g of oxalic acid and 38g of water to 80 ℃ for reaction for 6 hours to obtain the alkali-free accelerator.
The alkali-free accelerators obtained in examples 1 to 4 and comparative example 1 were tested for their performance and the results are shown in Table 1.
The testing materials, the setting time and the compression strength are tested by referring to national standard GBT35159-2017 accelerator for sprayed concrete. The cement used is P.O 42.5.5 cement produced by Jiangsu Helin cement Co.
The delamination value is: weighing 100ml of alkali-free accelerator into a 100ml measuring cylinder, standing for one week, and visually observing the stability, wherein the volume value of clear liquid appearing in the measuring cylinder is a layering value.
Viscosity number: 100ml of the alkali-free setting accelerator was weighed out and allowed to stand for one week, and the viscosity was measured using a Brookfield Brohler viscometer. And if the product is layered, the viscosity of the product is measured after the product is uniformly stirred.
Table 1 results of performance test of examples and comparative examples
As can be seen from table 1: the alkali-free accelerator only adopting the combination of the alcohol amine and the polyaluminium sulfate has poor comprehensive performance, and particularly, the stability cannot meet the requirement of the GBT35159-2017 standard. The gamma-methacryloxypropyltrimethoxysilane is used as a bridge, organic functional groups are introduced to polyaluminium sulfate and gamma-alumina, and then covalent bonds are directly formed with organic components, so that organic-inorganic hybrid compounding in the true sense is realized, the collision chance among inorganic particles is reduced, the organic chains can prevent the inorganic components from being excessively aggregated, the phenomenon of layering or precipitation of the product is prevented, and the excellent product with long service life and good construction performance is obtained. In addition, the introduced dimethyl diallyl ammonium chloride has higher charge density and proper molecular weight, and can be bonded and precipitated with calcium ions in cement, so that gypsum consumption is promoted, the hydration rate of C3A is increased, and the setting time of the product is shortened.
The foregoing shows and describes the basic principles, principal features and advantages of the present method. It will be understood by those skilled in the art that the present method is not limited to the embodiments described above, which are merely illustrative of the principles of the method, but that various changes and modifications may be made to the method without departing from the spirit and scope of the method, which changes and modifications are within the scope of the method as claimed. The scope of the method claimed is defined by the appended claims and equivalents thereof.
Claims (5)
1. A covalent bond type alkali-free accelerator is characterized by comprising the following components in percentage by mass:
inorganic component A40-50%
5 to 10 percent of alcohol amine
1 to 3 percent of organic acid
Organic component B12-15%
0.25 to 0.35 percent of catechol
The balance of water is water,
the sum of the mass percentages of the components is 100 percent;
the inorganic component A comprises the following components in percentage by mass
4-4.9% of polyaluminium sulfate with 200-300 meshes
0.1 to 1 percent of nano gamma-alumina
4 to 5 percent of silane coupling agent solution
95wt% ethanol aqueous solution balance
The sum of the mass percentages of the components is 100 percent,
wherein the solvent in the silane coupling agent solution is ethanol, the mass concentration of the silane coupling agent in the solution is 1-3 wt%, and the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane;
the organic component B comprises the following components in percentage by mass:
dimethyl diallyl ammonium chloride 20-25%
Acrylic acid 20-25%
0.2 to 1.2 percent of initiator
The balance of water is water,
the sum of the mass percentages of the components is 100 percent,
wherein the initiator is any one of ammonium persulfate, sodium persulfate and potassium persulfate.
2. The covalent bond type alkali-free accelerator according to claim 1, wherein the alcohol amine is diethanolamine or triethanolamine.
3. The alkali-free accelerator of covalent bond type according to claim 1, wherein the organic acid is lactic acid or oxalic acid.
4. The method for preparing the covalent bond type alkali-free accelerator as claimed in any one of claims 1 to 3, which comprises the following steps:
(1) adding 200-300 meshes of polyaluminium sulfate and nano gamma-alumina into 95wt% ethanol water solution, and then performing ultrasonic dispersion for 1h to obtain uniformly dispersed suspension; then adding the completely hydrolyzed silane coupling agent solution; stirring and reacting at 80 ℃ for 24h under the protection of nitrogen, then centrifugally separating, washing with ethanol for 3 times, and finally vacuum drying at 60 ℃ to obtain an inorganic component A;
(2) uniformly mixing dimethyl diallyl ammonium chloride, acrylic acid and water, and then adding an initiator to uniformly mix to obtain an organic component B;
(3) and (2) uniformly mixing the inorganic component A prepared in the step (1), alcohol amine, organic acid and water, heating to 60-80 ℃, then respectively adding the organic component B prepared in the step (2) and catechol, reacting for 2-6 h under heat preservation, and cooling to room temperature to obtain the covalent bond type alkali-free accelerator.
5. The method for using the covalent bond type alkali-free accelerator as claimed in any one of claims 1 to 3, wherein the covalent bond type alkali-free accelerator is used in the field of shotcrete, and the addition amount thereof is 6-9wt% of the cement amount.
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| CN113943122B (en) * | 2021-11-29 | 2023-01-10 | 中国铁路南宁局集团有限公司 | Alkali-free liquid accelerator capable of effectively preventing sprayed concrete from crystallizing and blocking drainage system and preparation method thereof |
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2018
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| JPH01157444A (en) * | 1987-12-12 | 1989-06-20 | Takenaka Komuten Co Ltd | Agent for accelerating and protecting bonding and method for bonding between inorganic materials |
| CN104558369A (en) * | 2014-12-29 | 2015-04-29 | 陕西长隆科技发展有限公司 | Preparation method of amphoteric clay inhibitor with low relative molecular mass |
| CN107827386A (en) * | 2017-11-20 | 2018-03-23 | 湖北工业大学 | Cement-based gelling material early-strength composition dispersant |
| CN108358497A (en) * | 2018-05-10 | 2018-08-03 | 江苏地基工程有限公司 | Novel foundation pit waterproof curtain added material alkali-free liquid accelerator and preparation method thereof |
Non-Patent Citations (1)
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| 二甲基二烯丙基氯化铵聚合物的研究进展及应用;向莹等;《北京印刷学院学报》;20080826;第16卷(第4期);第49-51页 * |
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