CN112723782B - Preparation method of early strength agent suitable for high-cold and high-altitude areas - Google Patents
Preparation method of early strength agent suitable for high-cold and high-altitude areas Download PDFInfo
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- CN112723782B CN112723782B CN202110120099.9A CN202110120099A CN112723782B CN 112723782 B CN112723782 B CN 112723782B CN 202110120099 A CN202110120099 A CN 202110120099A CN 112723782 B CN112723782 B CN 112723782B
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- early strength
- strength agent
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2682—Halogen containing polymers, e.g. PVC
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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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 provides a preparation method of an early strength agent suitable for alpine and high-altitude areas, which is characterized by comprising the following steps of: the method comprises the following steps: (1) r3NH2And R1‑C＝C‑R2Carrying out alkylation reaction on the-X under the action of a catalyst at the temperature of 120-150 ℃ to obtain a monomer M; (2) adding hydrogen peroxide into deionized water, stirring and dissolving, adding a monomer M, and uniformly stirring to obtain a material A; (3) adding ascorbic acid and a double-bond quaternary ammonium salt monomer into deionized water, and uniformly stirring to obtain a material B; (4) and dropwise adding the material B into the material A at a constant speed, and reacting at a constant temperature to obtain the early strength agent. The preparation method of the early strength agent suitable for the alpine and high-altitude areas adopts an aliphatic amine monomer and halogenated olefin to carry out alkylation reaction to obtain a monomer containing double bonds and N atoms, and then carries out free radical polymerization with a quaternary ammonium salt monomer containing double bonds to obtain the early strength polymer.
Description
Technical Field
The invention belongs to the field of concrete admixtures, and particularly relates to a preparation method of an early strength agent suitable for high-cold and high-altitude areas.
Background
In high and cold high-altitude areas, due to low air temperature and ground temperature and large day and night temperature difference, the concrete just poured is easy to suffer from freeze injury, so that the durability of the concrete is reduced, and the requirement on the additive with high early strength performance is more and more urgent.
The early strength agent can accelerate cement hydration, effectively shorten the concrete setting time and obviously improve the early strength of the concrete, thereby playing an irreplaceable role in the development of modern concrete. The early strength agents used at present are generally inorganic salts, organic small molecules and organic-inorganic complex. However, the inorganic salts have the problems that the mixing amount is high, the alkali content of the concrete is easily too high, and the durability of the concrete is reduced, and the chlorine-containing salts easily cause the corrosion of concrete reinforcing steel bars; the addition amount of small organic molecules such as triethanolamine is not easy to control, and the small organic molecules show early strength performance when added in a small amount, but once the addition amount is increased, the concrete is delayed due to the existence of hydroxyl, the initial and final setting time is influenced, the production period is prolonged, and even more, concrete quality accidents are caused. At present, polymeric early strength agent products appear in the market successively, and the effect is not obvious.
Therefore, the research and development of the early strength agent are hot spots of research in the industry, the synthesis research of the early strength product realized from the design of the polymer molecular structure is still in the initial exploration stage at present, and mature products are few, so the research on the high early strength agent has great economic, environmental and social significance.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing an early strength agent suitable for use in high-cold and high-altitude areas, which aims to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of an early strength agent suitable for alpine and high-altitude areas comprises the following steps:
(1)R3NH2and R1-C＝C-R2Carrying out alkylation reaction on the-X under the action of a catalyst at the temperature of 120-150 ℃ to obtain a monomer M;
(2) adding hydrogen peroxide into deionized water, stirring and dissolving, adding a monomer M, and uniformly stirring to obtain a material A;
(3) adding ascorbic acid and a double-bond quaternary ammonium salt monomer into deionized water, and uniformly stirring to obtain a material B;
(4) and dropwise adding the material B into the material A at a constant speed, and reacting at a constant temperature to obtain the early strength agent.
Further, R in the step (1)3Is straight chain alkyl with 2-4 carbon atoms; r in the step (1)1Is a hydrocarbon group with 0-2 carbon atoms; r in the step (1)2Is a hydrocarbon group with 0-2 carbon atoms; x in the step (1) is a halogen element.
Preferably, R in the step (1)3NH2At least one of ethylamine, propylamine or butylamine; r in the step (1)1-C＝C-R2-X is at least one of chloropropene, 1-chloro-2-butene or 4-chloro-1-butene.
Further, R in the step (1)3NH2And R1-C＝C-R2-the mass ratio of X is 1: 1.
further, the catalyst in the step (1) is NaBH4。
Further, the mass ratio of the deionized water to the hydrogen peroxide to the monomer M in the step (2) is 5: 0.3-0.5:5-6.
Further, the mass ratio of the deionized water to the ascorbic acid and the double-bond quaternary ammonium salt monomer in the step (3) is 5: 0.15-0.25:4-5.
Further, the double-bond quaternary ammonium salt monomer in the step (3) is at least one of diallyl dimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride or acryloyloxyethyl dimethyl benzyl ammonium chloride.
Further, the time of the dripping step in the step (4) is 2-3 hours, and the temperature is normal temperature; the time of the reaction step in the step (4) is 2 to 4 hours.
An early strength agent suitable for use in alpine and high-altitude areas, the early strength agent being prepared by the method of any one of claims 1 to 8.
The reaction formula of the preparation method of the early strength agent suitable for the alpine and high-altitude areas is shown as the formula (I) and the formula (II):
R3NH2+R1-C＝C-R2-X→R1-C＝C-R2-NH-R3
formula (I)
The preparation method of the early strength agent suitable for the alpine and high-altitude areas adopts the steps of carrying out alkylation reaction on aliphatic amine monomers and halogenated olefin to obtain a monomer containing double bonds and N atoms, then carrying out free radical polymerization on the monomer and a quaternary ammonium salt monomer containing the double bonds to obtain an early strength polymer, introducing the N atoms into the polymer structure, wherein the N atoms have 1 pair of unshared electrons, are easy to form covalent bonds with metal cations and form stable complexes with the metal ions, and the complexes form a plurality of soluble regions in a solution, so that the diffusion rate of hydration products is increased, and the C formed on the surfaces of clinker particles can be destroyed inevitably in the early stage of hydration3A. Calcium sulfoaluminate and other hydrate layer, increase of C3A、C4The AF is dissolved quickly, so that the reaction with the gypsum is accelerated, and calcium sulphoaluminate is rapidly generated. As the generation amount of calcium sulphoaluminate increases, the Ca content in the liquid phase is inevitably reduced2+、Al3+In addition, C is further increased3The hydration rate of S improves the early strength of the set cement, and the superposition effect of N atoms can promote the early strength of the concrete.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1 preparation of early Strength Agents
A preparation method of an early strength agent A suitable for alpine and high-altitude areas comprises the following steps:
(1)C2H5NH2and CH ═ CH-CH2-Cl in NaBH catalyst4Under the action of the action, carrying out alkylation reaction at 120 ℃ to obtain a monomer M;
(2) adding 0.3 part of hydrogen peroxide into 5 parts of deionized water, stirring for dissolving, adding 5 parts of monomer M, and uniformly stirring to obtain a material A;
(3) adding 0.15 part of ascorbic acid and 4 parts of diallyl dimethyl ammonium chloride into 5 parts of deionized water, and uniformly stirring to obtain a material B;
(4) and dropwise adding the material B into the material A at a constant speed for 2 hours, and reacting at a constant temperature for 2 hours to obtain the early strength agent A.
An early strength agent B is calcium nitrate (Weifang Changsheng nitrate Co., Ltd., manufactured by batch No. 2020102107).
An early strength agent C is triethanolamine (manufactured by 20200302035, Jinan Jiuyuixin chemical Co., Ltd.).
An early strength agent D is a polymer early strength agent (batch number: 20190425007 manufacturer: Xika (China) Co., Ltd.).
A preparation method of an early strength agent E comprises the following steps:
(1)C2H5NH2and CH ═ CH-CH2-Cl in NaBH catalyst4Under the action of the action, carrying out alkylation reaction at 120 ℃ to obtain a monomer M;
(2) and compounding the obtained 4 parts of monomer M with 5 parts of diallyl dimethyl ammonium chloride to obtain the early strength agent D.
Example 2 concrete test
Two common brands of cement are selected for concrete test, no early strength agent is added as a blank control, and the concrete mixing ratio is as follows:
1. jidong 42.5 cement: 250, mineral powder: 60, fly ash: 80, sand: 780, stone: 1070, water: 160, mixing amount of the water reducing agent: 2.0%, early strength agent: 0.2 percent of the addition of the cementing material (cement, mineral powder and fly ash); and (3) test environment: the temperature is 22 ℃ and the humidity is 60 percent.
The results are shown in Table 1.
TABLE 1 detection result of concrete performance of Jidong 42.5 cement
2. 42.5 cement of golden corner: 250, mineral powder: 60, fly ash: 80, sand: 780, stone: 1070, water: 165, water reducer mixing amount: 2.0 percent; early strength agent: 0.2 percent of the addition of the cementing material (cement, mineral powder and fly ash); and (3) test environment: the temperature is 22 ℃ and the humidity is 60 percent.
The results are shown in Table 2.
Table 2: detection result of performances of 42.5 cement-concrete
According to the analysis of the test data, the early strength agent prepared by the invention has obvious improvement on the early strength of 1 day and 3 days in two types of cement, and the compression strength of 7 days and 28 days in the later period does not have the phenomenon of retraction.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of an early strength agent suitable for alpine and high-altitude areas is characterized by comprising the following steps: the method comprises the following steps:
(1)R3NH2and R1-C＝C-R2Carrying out alkylation reaction on the-X under the action of a catalyst at the temperature of 120-150 ℃ to obtain a monomer M;
(2) adding hydrogen peroxide into deionized water, stirring and dissolving, adding a monomer M, and uniformly stirring to obtain a material A;
(3) adding ascorbic acid and a double-bond quaternary ammonium salt monomer into deionized water, and uniformly stirring to obtain a material B;
(4) and dropwise adding the material B into the material A at a constant speed, and reacting at a constant temperature to obtain the early strength agent.
2. The preparation method of the early strength agent for the alpine and high-altitude areas according to claim 1, wherein the early strength agent comprises the following components: r in the step (1)3Is straight chain alkyl with 2-4 carbon atoms; r in the step (1)1Is a hydrocarbon group with 0-2 carbon atoms; r in the step (1)2Is a hydrocarbon group with 0-2 carbon atoms; x in the step (1) is a halogen element.
3. The preparation method of the early strength agent for the alpine and high-altitude areas according to claim 2, wherein the early strength agent comprises the following components: r in the step (1)3NH2At least one of ethylamine, propylamine or butylamine; r in the step (1)1-C＝C-R2-X is at least one of chloropropene, 1-chloro-2-butene or 4-chloro-1-butene.
4. The preparation method of the early strength agent for the alpine and high-altitude areas according to claim 1, wherein the early strength agent comprises the following components: r in the step (1)3NH2And R1-C＝C-R2-the mass ratio of X is 1: 1.
5. the preparation method of the early strength agent for the alpine and high-altitude areas according to claim 1, wherein the early strength agent comprises the following components: the catalyst in the step (1) is NaBH4。
6. The preparation method of the early strength agent for the alpine and high-altitude areas according to claim 1, wherein the early strength agent comprises the following components: the mass ratio of the deionized water to the hydrogen peroxide to the monomer M in the step (2) is 5: 0.3-0.5:5-6.
7. The preparation method of the early strength agent for the alpine and high-altitude areas according to claim 1, wherein the early strength agent comprises the following components: the mass ratio of the deionized water to the ascorbic acid and the double-bond quaternary ammonium salt monomer in the step (3) is 5: 0.15-0.25:4-5.
8. The preparation method of the early strength agent for the alpine and high-altitude areas according to claim 1, wherein the early strength agent comprises the following components: the double-bond quaternary ammonium salt monomer in the step (3) is at least one of diallyl dimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride or acryloyloxyethyl dimethyl benzyl ammonium chloride.
9. The preparation method of the early strength agent for the alpine and high-altitude areas according to claim 1, wherein the early strength agent comprises the following components: the time of the dripping step in the step (4) is 2-3 hours, and the temperature is normal temperature; the time of the reaction step in the step (4) is 2 to 4 hours.
10. An early strength agent suitable for high-cold and high-altitude areas, which is characterized in that: the early strength agent is prepared by the method of any one of claims 1-8.
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Citations (6)
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| KR950017810A (en) * | 1993-12-10 | 1995-07-20 | 박순기 | Solid powder crude steel composition for soil and cement condensation |
| EP2248780A1 (en) * | 2009-05-06 | 2010-11-10 | BK Giulini GmbH | Set- and hardening accelerator |
| CN102126840A (en) * | 2011-03-02 | 2011-07-20 | 陈子川 | Low-temperature concrete early strength agent |
| CN107151294A (en) * | 2017-06-08 | 2017-09-12 | 中建材中岩科技有限公司 | Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN107827386A (en) * | 2017-11-20 | 2018-03-23 | 湖北工业大学 | Cement-based gelling material early-strength composition dispersant |
| CN110229285A (en) * | 2019-07-22 | 2019-09-13 | 北京慕湖房地产开发股份有限公司 | A kind of preparation method of Early-strength polycarboxylate superplasticizer |
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2021
- 2021-01-28 CN CN202110120099.9A patent/CN112723782B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950017810A (en) * | 1993-12-10 | 1995-07-20 | 박순기 | Solid powder crude steel composition for soil and cement condensation |
| EP2248780A1 (en) * | 2009-05-06 | 2010-11-10 | BK Giulini GmbH | Set- and hardening accelerator |
| CN102126840A (en) * | 2011-03-02 | 2011-07-20 | 陈子川 | Low-temperature concrete early strength agent |
| CN107151294A (en) * | 2017-06-08 | 2017-09-12 | 中建材中岩科技有限公司 | Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN107827386A (en) * | 2017-11-20 | 2018-03-23 | 湖北工业大学 | Cement-based gelling material early-strength composition dispersant |
| CN110229285A (en) * | 2019-07-22 | 2019-09-13 | 北京慕湖房地产开发股份有限公司 | A kind of preparation method of Early-strength polycarboxylate superplasticizer |
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