CN113185686A - Preparation method of air entraining agent - Google Patents
Preparation method of air entraining agent Download PDFInfo
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- CN113185686A CN113185686A CN202110480635.6A CN202110480635A CN113185686A CN 113185686 A CN113185686 A CN 113185686A CN 202110480635 A CN202110480635 A CN 202110480635A CN 113185686 A CN113185686 A CN 113185686A
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- reaction kettle
- air entraining
- entraining agent
- stirring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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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
- C04B24/243—Phosphorus-containing polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
-
- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/304—Air-entrainers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Mixers Of The Rotary Stirring Type (AREA)
Abstract
The application relates to the technical field of composite material preparation, and particularly discloses a preparation method of an air entraining agent, wherein the parts are parts by mass, and the preparation method of the air entraining agent comprises the following steps: adding an initiator and sodium hydroxide into a reaction kettle A under the stirring state, heating to 65-75 ℃, vacuumizing and stirring for 30-90min, putting ethylene oxide into a reaction kettle B, dropwise adding ethylene oxide into the reaction kettle A from the reaction kettle B, heating the reaction kettle A to 120-130 ℃, and maintaining the system pressure of the reaction kettle A under a medium-pressure environment; slowly dripping the residual ethylene oxide in the reaction kettle B into the reaction kettle A to obtain an intermediate A; adding the intermediate A, phosphoric acid and a cosolvent into a cleaned reaction kettle A, heating to 120-130 ℃, and stirring for 15-18 h; cooling, concentrating and cleaning to obtain the air entraining agent. The purpose of this patent is to solve air entraining agent foam stabilization effect among the prior art not good, need add the problem of more air entraining agent in order to improve the workability of concrete.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method of an air entraining agent.
Background
The air entraining agent is the earliest additive applied to concrete, and is applied to the concrete by ancient people in China as early as the construction period of the Qin great wall. With the progress of the times and the development of science and technology, the air entraining agent is gradually applied to the fields of water conservancy, ports, high-speed rails, bridges and the like. The air entraining agent is an additive capable of introducing a large amount of uniform micro bubbles in the stirring process of a concrete mixture, and the stability and the quantity of the introduced bubbles are two important indexes for measuring the air entraining agent. The development of a novel high-performance air entraining agent and the improvement of the comprehensive performance of the air entraining agent have great significance for the development of the construction industry in China. The existing air entraining agent in the market has poor foam stabilizing effect, more air entraining agent needs to be added to improve the workability of concrete, and the strength of the concrete is reduced by adding more air entraining agent to influence the hardened concrete structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an air entraining agent, which aims to solve the problems that the air entraining agent in the prior art has poor foam stabilizing effect and needs to be added with more air entraining agent to improve the workability of concrete.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the air entraining agent comprises the following steps:
step 1: under the stirring state, adding 18-22 parts of initiator and 0.03-0.05 part of sodium hydroxide into a reaction kettle A, heating to 65-75 ℃, and then vacuumizing and stirring for 30-90 min;
step 2: putting 90-91 parts of ethylene oxide into a dropwise adding tank, and dropwise adding 1-2 parts of ethylene oxide into a reaction kettle A from a reaction kettle B;
and step 3: heating the reaction kettle A to 120-130 ℃, and maintaining the pressure of the reaction kettle A at 0.2-0.3 MPa;
and 4, step 4: slowly dripping the residual ethylene oxide in the reaction kettle B into the reaction kettle A to obtain an intermediate A;
and 5: adding 9-11 parts of the intermediate A, 1-2 parts of phosphoric acid and 2-5 parts of cosolvent into a reaction kettle C, heating to 120-;
step 6: stopping stirring, cooling to room temperature, concentrating under low pressure, and cleaning to obtain the air entraining agent.
The beneficial effect that this scheme produced is:
1. the air entraining agent prepared by the scheme is low in mixing amount and remarkable in air entraining effect, and the situation that the strength of concrete is reduced too much due to more air entraining agent is reduced;
2. the air entraining agent prepared by the scheme has excellent foam stabilizing performance; after the air entraining agent prepared by the scheme is added into concrete, the workability of the concrete can be obviously improved, the on-site construction efficiency is effectively improved, and the production cost is reduced.
Further, the initiator in the step 1 is 4-n-nonylphenol. 4-n-nonyl phenol is used as an initiator, the surface tension of the air entraining agent synthesized by the method is lower, and the surface tension of the aqueous solution can be reduced to a greater extent after the solution is added, so that a better air entraining effect is achieved.
Further, the total dropping time of ethylene oxide in step 4 is at least 4 hours. The dropping time is controlled to be more than 4h, and the conversion rate of the ethylene oxide is effectively improved.
Further, the mass concentration of phosphoric acid in step 5 was 85%. The 85 percent industrial grade phosphoric acid is easy to purchase and convenient to produce.
Further, a stirring blade is rotationally connected in the reaction kettle A, and the distance between the stirring blade and the bottom of the reaction kettle A is one tenth of the inner diameter of the reaction kettle A. The distribution of the turbulence kinetic energy is more uniform through the distribution of the stirring blades, the distribution of dead zones in the stirring kettle is reduced, and the stirring and mixing efficiency is greatly improved. Prevent the stirring blade from being too close to or too far away from the bottom of the reaction kettle to influence the stirring state of the mixed liquid and the uniform degree of mixing.
Furthermore, 4 stirring blades are arranged in the vertical direction and are crossed; the stirring blades are Z-shaped and are rotationally and symmetrically arranged along the stirring shaft. The Z-shaped stirring blades which are designed in vertical rotational symmetry enable the mixed liquid to be mixed more uniformly up and down.
Drawings
Fig. 1 shows the effect of air entraining agents on the air content of concrete.
Figure 2 is a graph of air entraining agent bubble height.
FIG. 3 is a side view of the stirring vane.
FIG. 4 is a plan view of the stirring vanes.
FIG. 5 is a graph showing the change in dead volume fraction with Reynolds number in a laminar flow zone stirred tank.
Detailed Description
The following is further detailed by way of specific embodiments:
reference numerals in the drawings of the specification include: a stirring shaft 1, a horizontal shaft 2 and a stirring blade 3.
Example 1: the preparation method of the air entraining agent is carried out according to the following steps:
step 1: under the stirring state, adding 18 parts of 4-n-nonyl phenol and 0.04 part of sodium hydroxide into a reaction kettle A provided with a self-made multi-blade stirring paddle, heating to 70 ℃, vacuumizing and stirring for 30-90min, wherein the distance between the bottom of the self-made multi-blade stirring paddle reaction kettle is 20mm, and the inner diameter of the reaction kettle is 200 mm;
step 2: putting 90.6 parts of ethylene oxide into a reaction kettle B, and dropwise adding 1 part of ethylene oxide into the reaction kettle A from the reaction kettle B;
and step 3: heating the reaction kettle A to 120 ℃, and maintaining the system pressure at 0.2 MPa;
and 4, step 4: slowly dripping the residual ethylene oxide in the reaction kettle B into the reaction kettle A, and controlling the total dripping time to be 4 hours to obtain an intermediate A;
and 5: adding 10 parts of the intermediate A, 1 part of 85% phosphoric acid and 4 parts of methyl oleate into a reaction kettle C, heating to 120 ℃, and stirring for 15 hours;
step 6: stopping stirring, cooling to room temperature, concentrating under low pressure, and cleaning to obtain the air entraining agent.
Example 2: this embodiment differs from example 1 in that: in step 1, 22 parts of 4-n-nonylphenol are used.
Example 3: this embodiment differs from embodiment 1 or 2 in that: the total dropping time of ethylene oxide in step 4 was 5 hours.
Example 4: this embodiment differs from examples 1-3 in that: the portion of 85% phosphoric acid in step 5 is 2 portions.
Table 1 comparison of air entraining agent parametric bubble results for each example
The beneficial effects of the invention are verified by the following tests, which are realized according to the following steps:
s1: the experimental concrete compounding ratio is shown in table 1, and the experimental concrete is prepared by stirring according to table 1 and the performance is tested by adding air entraining agents with different mixing amounts.
TABLE 2 concrete mix proportion for experiments
| Name (R) | Jinjiu cement P.O 42.5 | Fine aggregate | Coarse aggregate | Water (W) |
| Content (kg) | 360 | 756 | 1052 | 175 |
S2: testing the gas content of the concrete according to the method in GB/T50080-2016 standard for testing the performance of common concrete mixtures, wherein the final result is shown in figure 1;
s3: the air entraining agent prepared according to example 1 was diluted to 0.05% using ultrapure water, and the change in height of foam of the air entraining agent with time was analyzed using a foam dynamic analyzer (DFA100) while comparing the change in height of foam of the conventional HT-3 air entraining agent with time, and the results are shown in fig. 2.
As can be seen from fig. 1 and 2, after the air entraining agent prepared in example 1 is added into the concrete, the air content of the concrete is significantly improved, and as can be seen from fig. 2, the foaming speed and the foam height of the air entraining agent prepared in the patent are higher than those of the commercially available conventional HT-3 air entraining agent, which indicates that the air entraining agent prepared in the patent has an excellent foaming effect; in addition, as can be seen from fig. 2, the bubble height of the novel air entraining agent prepared by the method is not obviously reduced within 800 seconds, which shows that the bubble stabilizing effect of the air entraining agent prepared by the method is excellent.
As shown in fig. 3 and 4, a stirring shaft 1 is rotationally connected in the reaction kettle a, the middle part of the stirring shaft 1 is fixedly connected with a cross shaft 2, the cross shaft 2 is vertically connected with stirring blades 3 through bolts, and the stirring shaft 1, the cross shaft 2 and the stirring blades 3 jointly form a self-made stirring paddle; the stirring blades are arranged along the vertical direction, and 4 stirring blades 3 are arranged in a cross manner; the stirring blades 3 are Z-shaped and are arranged along the stirring shaft in a rotating and symmetrical mode, namely the directions of the Z-shaped stirring blades on the same horizontal line are consistent, and the mixed liquid is mixed more uniformly up and down due to the Z shape; the height of the stirring blade is 229mm, the length of the blade in the horizontal direction of the Z-shaped stirring blade is 27mm, and the distance between the vertical shafts of the two stirring blades on the same horizontal line is 100 mm. The distribution of turbulent kinetic energy is more uniform through the dispersion layout of the multiple blades, the distribution of dead zones in the stirring kettle is reduced, and the stirring and mixing efficiency is greatly improved; the distance between the stirring blade 3 and the bottom of the reaction kettle A is one tenth of the inner diameter of the reaction kettle A, and if the inner diameter of the reaction kettle A is 200mm, the distance between the stirring blade and the bottom of the reaction kettle A is 20 mm; prevent that stirring leaf 3 from being too close or too far away from the reation kettle bottom, influencing mixed liquid stirring state and misce bene degree.
The beneficial effects of the stirring shaft and the stirring blades in the scheme are verified through the following tests:
a dynamic kinetic energy transport sub-lattice stress model in a large vortex simulation method is adopted to simulate a stirring system on an Ansys Fluent 17.0, and the grid precision in the large vortex simulation calculation process is evaluated through a Kolmogorov scale and a Taylor scale:
η＝(ν3/ε)0.25
λ＝(15νu’2/ε)0.5
the Taylor scale obtained by calculation is 4.5mm, the Taylor scale is in the same magnitude as the grid analysis scale (0.11-5.05 mm), the Kolmogorov scale is 0.10mm, and the Kolmogorov scale is almost consistent with the minimum grid analysis scale, so that the grid simulation precision is reliable.
The volume fractions of dead zones of the stirring shaft and the stirring blades and a common commercial MaxBlend stirring paddle in the prior art under different Reynolds numbers are shown in figure 5, the volume fractions of the dead zones are reduced along with the increase of the Re value, and the dead zones of the stirring shaft and the stirring blades are smaller; thereby effectively improving the mixing uniformity of the mixed liquid.
The above description is only an example of the present invention, and the common general knowledge of the known specific structures and characteristics in the embodiments is not described herein. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practical applicability of the present invention. The scope of the claims of the present application shall be defined by the claims, and the description of specific embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (6)
1. A preparation method of the air entraining agent is characterized by comprising the following steps: the air entraining agent is prepared from the following components in parts by mass:
step 1: under the stirring state, adding 18-22 parts of initiator and 0.03-0.05 part of sodium hydroxide into a reaction kettle A, heating to 65-75 ℃, and then vacuumizing and stirring for 30-90 min;
step 2: putting 90-91 parts of ethylene oxide into a reaction kettle B, and dropwise adding 1-2 parts of ethylene oxide into the reaction kettle A from the reaction kettle B;
and step 3: heating the reaction kettle A to 120-130 ℃, and maintaining the pressure of the reaction kettle A at 0.2-0.3 MPa;
and 4, step 4: slowly dripping the residual ethylene oxide in the reaction kettle B into the reaction kettle A to obtain an intermediate A;
and 5: adding 9-11 parts of the intermediate A, 1-2 parts of phosphoric acid and 2-5 parts of cosolvent into a cleaned reaction kettle A, heating to 120-130 ℃, and stirring for 15-18 h;
step 6: stopping stirring, cooling to room temperature, concentrating under low pressure, and cleaning to obtain the air entraining agent.
2. The method for preparing the air entraining agent according to claim 1, wherein: the initiator in the step 1 is 4-n-nonylphenol.
3. The method for preparing the air entraining agent according to claim 1, wherein: the total dropping time of the ethylene oxide in the step 4 is at least 4 h.
4. The method for preparing the air entraining agent according to claim 1, wherein: the mass concentration of the phosphoric acid in the step 5 is 85%.
5. The method for preparing the air entraining agent according to claim 1, wherein: the reaction kettle A is rotatably connected with a stirring shaft, the stirring shaft is detachably connected with a stirring blade, and the distance between the stirring blade and the bottom of the reaction kettle A is one tenth of the inner diameter of the reaction kettle A.
6. The method for preparing the air entraining agent according to claim 6, wherein: the stirring blades are arranged in the vertical direction, and 4 stirring blades are arranged in a cross manner; the stirring blades are Z-shaped and are arranged along the stirring shaft in a rotational symmetry manner.
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| CN202110480635.6A CN113185686A (en) | 2021-04-30 | 2021-04-30 | Preparation method of air entraining agent |
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| CN202110480635.6A CN113185686A (en) | 2021-04-30 | 2021-04-30 | Preparation method of air entraining agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114804750A (en) * | 2022-05-10 | 2022-07-29 | 咸阳鼎诚建材有限公司 | Anti-freezing concrete and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1512252A (en) * | 1974-06-06 | 1978-05-24 | Anneliese Zementwerke Ag | Process for the manufacture of cements of high initial strength |
| GB1534532A (en) * | 1975-10-13 | 1978-12-06 | Albright & Wilson | Production of aerated cement based building materials |
| CN107021668A (en) * | 2017-05-14 | 2017-08-08 | 张芸 | A kind of preparation method of concrete composite air entraining agent |
-
2021
- 2021-04-30 CN CN202110480635.6A patent/CN113185686A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1512252A (en) * | 1974-06-06 | 1978-05-24 | Anneliese Zementwerke Ag | Process for the manufacture of cements of high initial strength |
| GB1534532A (en) * | 1975-10-13 | 1978-12-06 | Albright & Wilson | Production of aerated cement based building materials |
| CN107021668A (en) * | 2017-05-14 | 2017-08-08 | 张芸 | A kind of preparation method of concrete composite air entraining agent |
Non-Patent Citations (3)
| Title |
|---|
| MA, JF等: "Synthesis, characterization, and performance of novel phosphate-modified polymers as air-entraining agents", 《CONSTRUCTION AND BUILDING MATERIALS》 * |
| 方云辉: "新型混凝土专用引气剂的研制", 《福建建材》 * |
| 杨春柏: "《塑料成型基础》", 31 July 1999, 中国轻工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114804750A (en) * | 2022-05-10 | 2022-07-29 | 咸阳鼎诚建材有限公司 | Anti-freezing concrete and preparation method thereof |
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