CN108864389B - Preparation method of viscosity-reducing sulfamate water reducer - Google Patents
Preparation method of viscosity-reducing sulfamate water reducer Download PDFInfo
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- CN108864389B CN108864389B CN201810851262.7A CN201810851262A CN108864389B CN 108864389 B CN108864389 B CN 108864389B CN 201810851262 A CN201810851262 A CN 201810851262A CN 108864389 B CN108864389 B CN 108864389B
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a preparation method of a viscosity-reducing sulfamate water reducer, which comprises the following steps: (1) adding sulfanilic acid, a phenolic compound, a viscosity reducer and water into a reaction kettle, heating, stirring and dissolving, then continuously heating to a temperature not more than 80 ℃, starting to slowly dropwise add the condensing agent, completing dropwise addition within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving the temperature for 1-2 hours after dropwise addition; (2) adding an alkaline regulator into the material obtained in the step (1) to regulate the pH value to 9-10, and continuing to react; (3) adding a reaction terminator and water into the material obtained in the step (2), continuously heating to 80-90 ℃, and then preserving heat; (4) and (4) cooling the material obtained in the step (3) to room temperature, and adjusting the pH value to 7-8 to obtain the material. According to the invention, the viscosity reducer is introduced, and the molecules of the viscosity reducer are provided with phosphate radicals with high hydrophilic characteristics, so that a stable hydration film can be formed on the surfaces of the particles, thereby facilitating the sliding of the particles, effectively reducing the cohesive property of clay in concrete and enabling the concrete to have high fluidity.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a viscosity-reducing sulfamate water reducer.
Background
In recent years, with the rapid development of concrete technology towards high strength, green and high performance, higher and more comprehensive requirements are also provided for the water reducing agent which is an important component in concrete, and the traditional water reducing agent cannot meet the requirements. Although the traditional naphthalene and melamine high-efficiency water reducing agents have mature processes, the traditional naphthalene and melamine high-efficiency water reducing agents show obvious defects in the aspect of preparing high-performance concrete due to low water reducing rate, quick slump loss, poor adaptability to cement and the like, and bring inconvenience to concrete construction; the polycarboxylate superplasticizer has high water reducing rate and strong plastic-retaining capacity, and the structure and the function of the polycarboxylate superplasticizer have strong designability, so the polycarboxylate superplasticizer is considered as a regeneration product of the high-efficiency superplasticizer. However, a large number of engineering examples and researches show that the polycarboxylic acid water reducing agent cannot well solve the problem of high concrete viscosity caused by low water-cement ratio; the polycarboxylate water reducing agent is influenced most by the clay, and the polycarboxylate water reducing agent molecules can be embedded into the interlayer structure of the clay to consume a large amount of the water reducing agent, so that the fluidity of concrete is influenced, the cohesiveness of a mixture is increased, and pumping and construction are not facilitated.
The sulfamate high-efficiency water reducing agent is mainly prepared by condensing sulfanilic acid, monocyclic aromatic derivative phenol compounds and formaldehyde under acidic or alkaline conditions, is a high-efficiency water reducing agent, is different from other high-efficiency water reducing agents in that the sulfamate high-efficiency water reducing agent has a certain side chain in structure, is similar to a polycarboxylic acid water reducing agent in adsorption mode, is in tooth type, lead type and the like, is not in plane adsorption of other high-efficiency water reducing agents, and has the advantages of high water reducing rate, capability of improving the workability and durability of concrete and the like. The effect of clay on sulfamate superplasticizers is relatively small compared to polycarboxylic acid water reducers, but the effect is still present. Therefore, the viscosity reduction type sulfamate water reducer is developed, the problems that the viscosity of the existing sulfamate water reducer is increased and the dispersing performance is reduced due to the influence of clay are solved, the problem that the low water-cement ratio concrete is difficult to construct due to the increase of the viscosity is solved, and the viscosity reduction type sulfamate water reducer has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a viscosity-reducing sulfamate water reducer.
The technical scheme of the invention is as follows:
a preparation method of a viscosity-reducing sulfamate water reducer comprises the following steps:
(1) adding sulfanilic acid, a phenolic compound, a viscosity reducer and water into a reaction kettle, heating to 70 ℃, stirring for dissolving, then continuously heating to a temperature not more than 80 ℃, starting to slowly dropwise add the condensing agent, completing dropwise addition within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving heat for 1-2 hours after dropwise addition; the phenolic compound is at least one of phenol, bisphenol A, bisphenol S, paracresol, metacresol and resorcinol; the structural formula of the viscosity reducer is
Wherein n is 5-30; the condensing agent is one or two of formaldehyde, acetaldehyde and furfural;
(2) adding an alkaline regulator into the material obtained in the step (1) to regulate the pH value to 9-10, and continuing to react for 1.5-2.5 h;
(3) adding a reaction terminator and water into the material obtained in the step (2), continuously heating to 80-90 ℃, and then preserving heat for 1.5-2.5 h;
(4) and (4) cooling the material obtained in the step (3) to room temperature, and adjusting the pH value to 7-8 to obtain the material.
In a preferred embodiment of the invention, the alkaline modifier is sodium hydroxide and/or potassium hydroxide.
In a preferred embodiment of the present invention, the reaction terminator is at least one of sodium bisulfite, sodium metabisulfite, and sodium sulfite.
In a preferred embodiment of the present invention, in the step (3), the mass ratio of the reaction terminator to the water is 8-12: 30.
More preferably, in the step (1), the mass ratio of the sulfanilic acid, the phenolic compound, the viscosity reducer, the water and the condensing agent is 35-60: 30-70: 5-30: 200: 50-90.
More preferably, in the step (1), the mass ratio of the sulfanilic acid, the phenolic compound, the viscosity reducer, the water and the condensing agent is 35-55: 30-67: 6-28: 200: 52-85.
Still more preferably, in the step (1), the mass ratio of the sulfanilic acid, the phenolic compound, the viscosity reducer, the water and the condensing agent is 40-55: 35-67: 6-25: 200: 52-80.
The invention has the beneficial effects that:
1. the invention introduces the viscosity reducer, adds the phenol compound, the condensing agent, the sulfanilic acid and other multi-component condensation polymerization to form a multi-branched net-shaped molecular structure, and water reducer molecules are subjected to three-dimensional adsorption on the surface of cement particles, so that the concrete has good dispersibility and dispersion retention capability.
2. The viscosity reducer introduced by the invention has divalent phosphate radicals, has high hydrophilic property, is easy to be combined with water molecules in a hydrogen bond form, can form a stable hydration film on the surface of particles, is beneficial to the sliding of the particles, effectively reduces the cohesiveness of concrete, and enables the concrete to have high fluidity.
3. The invention adopts the cheap sodium bisulfite/sodium metabisulfite/sodium sulfite and the like to absorb the free formaldehyde in the synthesis of the sulfamate water reducer, thereby not only preventing the continuation of the polycondensation reaction, avoiding the reduction of the product performance caused by the overlarge molecular weight of the water reducer, but also reducing the pollution to the environment.
4. The invention has the advantages of simple production process, short production period, mild reaction temperature, controllable production operation and stable product quality.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
A preparation method of a viscosity-reducing sulfamate water reducer comprises the following steps:
(1) adding 55 parts by mass of sulfanilic acid, 67 parts by mass of bisphenol A, 25 parts by mass of a viscosity reducer and 200 parts by mass of water into a reaction kettle, heating to 70 ℃, stirring for dissolving, continuously heating to a temperature not higher than 80 ℃, then slowly dropwise adding 62 parts by mass of a formaldehyde condensing agent, completing dropwise adding within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving the heat for 1-2 hours after dropwise adding of the condensing agent is completed;
(2) after the heat preservation is finished, adding about 20 parts of sodium hydroxide solution to adjust the pH value of the system to 9-10, and continuing to react for 2 hours;
(3) after the reaction is finished, adding 12 parts of sodium bisulfite and 30 parts of water, continuously heating to 80-90 ℃, and keeping the temperature for 2 hours;
(4) and cooling to room temperature, and adjusting the pH value of the system to 7-8 to obtain the product.
Example 2
A preparation method of a viscosity-reducing sulfamate water reducer comprises the following steps:
(1) adding 42 parts by mass of sulfanilic acid, 35 parts by mass of phenol, 10 parts by mass of viscosity reducer and 200 parts by mass of water into a reaction kettle, heating to 70 ℃, stirring for dissolving, continuously heating to a temperature not higher than 80 ℃, then slowly dropwise adding 80 parts by mass of acetaldehyde condensing agent, completing dropwise adding within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving the temperature for 1-2 hours after dropwise adding of the condensing agent is completed;
(2) after the heat preservation is finished, adding about 15 parts of potassium hydroxide solution to adjust the pH value of the system to 9-10, and continuing to react for 2 hours;
(3) after the reaction is finished, adding 10 parts of sodium sulfite and 30 parts of water, continuously heating to 80-90 ℃, and preserving heat for 2 hours;
(4) and cooling to room temperature, and adjusting the pH value of the system to 7-8 to obtain the product.
Example 3
A preparation method of a viscosity-reducing sulfamate water reducer comprises the following steps:
(1) adding 50 parts by mass of sulfanilic acid, 47 parts by mass of m-xylenol, 22 parts by mass of a viscosity reducer and 200 parts by mass of water into a reaction kettle, heating to 70 ℃, stirring for dissolving, continuously heating to a temperature not higher than 80 ℃, then slowly dropwise adding 70 parts by mass of a condensing agent (20 parts by mass of furfural and 50 parts by mass of formaldehyde), dropwise adding within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving the heat for 1-2 hours after dropwise adding of the condensing agent is completed;
(2) after the heat preservation is finished, adding about 18 parts of sodium hydroxide solution to adjust the pH value of the system to 9-10, and continuing to react for 2 hours;
(3) after the reaction is finished, adding 8 parts of sodium metabisulfite and 30 parts of water, continuously heating to 80-90 ℃, and preserving heat for 2 hours;
(4) and cooling to room temperature, and adjusting the pH value of the system to 7-8 to obtain the product.
Example 4
A preparation method of a viscosity-reducing sulfamate water reducer comprises the following steps:
(1) adding 40 parts by mass of sulfanilic acid, 15 parts by mass of bisphenol S, 20 parts by mass of phenol, 6 parts by mass of viscosity reducer and 200 parts by mass of water into a reaction kettle, heating to 70 ℃, stirring for dissolution, continuously heating to a temperature not higher than 80 ℃, then slowly dropwise adding 52 parts by mass of formaldehyde, completing dropwise adding within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving the heat for 1-2 hours after dropwise adding of the condensing agent is completed;
(2) after the heat preservation is finished, adding about 13 parts of sodium hydroxide solution to adjust the pH value of the system to 9-10, and continuing to react for 2 hours;
(3) after the reaction is finished, adding 8 parts of sodium bisulfite and 30 parts of water, continuously heating to 80-90 ℃, and keeping the temperature for 2 hours;
(4) and cooling to room temperature, and adjusting the pH value of the system to 7-8 to obtain the product.
The modified sulfamate water reducers prepared in examples 1 to 4 were tested: comparing the sample synthesized in the embodiment 1-4 with a commercially available sulfamate water reducer ASP, and detecting the water reduction rate of the viscosity-reducing sulfamate water reducer and the influence of the viscosity-reducing sulfamate water reducer on fresh concrete by using standard cement according to a method specified in GB 8076-2008 concrete Admixture. The concrete mixing proportion is as follows: cement 430kg/m330kg/m of fly ash390kg/m of mineral powder3700kg/m of sand3Stone 1050kg/m3155kg/m of water3. The concrete viscosity is quantified by measuring the flow-empty time of the slump cone, and the shorter the flow-empty time is, the smaller the concrete viscosity is, the concrete viscosity is determined by the following specific method: controlling the initial expansion of each sample to be equal by adjusting the mixing amount of the water reducing agent, inverting the slump cone, adding a rapidly openable sealing cover at the bottom of the slump cone, filling the slump cone with concrete, leveling the slump cone, and inverting the slump coneFixed on a bench, the bottom of which is not less than 500mm from the ground, the bottom cover is quickly slid off, and the concrete flow time is measured with a stopwatch, the results are shown in table 1.
TABLE 1 concrete Performance test results
As can be seen from Table 1, compared with the commercially available products, the viscosity reduction type sulfamate water reducer prepared by the method has the advantages of high water reduction rate, good slump retention performance, good mixture workability, high flow rate, soft materials and the like, and the collapse emptying time of the examples 1-4 is obviously shorter than that of the commercially available products, so that the sulfamate water reducer prepared by the method can effectively reduce the viscosity of concrete and improve the construction performance of the concrete.
It will be appreciated by those skilled in the art that the technical parameters and raw material components of the present invention can be changed within the following ranges to obtain the same or similar technical effects as the above examples, and still fall within the protection scope of the present invention:
a preparation method of a viscosity-reducing sulfamate water reducer comprises the following steps:
(1) adding sulfanilic acid, a phenolic compound, a viscosity reducer and water into a reaction kettle, heating to 70 ℃, stirring for dissolving, then continuously heating to a temperature not more than 80 ℃, starting to slowly dropwise add the condensing agent, completing dropwise addition within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving heat for 1-2 hours after dropwise addition; the phenolic compound is at least one of phenol, bisphenol A, bisphenol S, paracresol, metacresol and resorcinol; the structural formula of the viscosity reducer is
Wherein n is 5-30; the condensing agent is one or two of formaldehyde, acetaldehyde and furfural;
(2) adding an alkaline regulator into the material obtained in the step (1) to regulate the pH value to 9-10, and continuing to react for 1.5-2.5 h;
(3) adding a reaction terminator and water into the material obtained in the step (2), continuously heating to 80-90 ℃, and then preserving heat for 1.5-2.5 h;
(4) and (4) cooling the material obtained in the step (3) to room temperature, and adjusting the pH value to 7-8 to obtain the material.
The alkaline regulator is sodium hydroxide and/or potassium hydroxide. The reaction terminator is at least one of sodium bisulfite, sodium metabisulfite and sodium sulfite. In the step (1), the mass ratio of the sulfanilic acid, the phenolic compound, the viscosity reducer, the water and the condensing agent is 35-60: 30-70: 5-30: 200: 50-90, preferably, the mass ratio of the sulfanilic acid, the phenolic compound, the viscosity reducer, the water and the condensing agent is 35-55: 30-67: 6-28: 200: 52-85.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. A preparation method of a viscosity-reducing sulfamate water reducer is characterized by comprising the following steps: the method comprises the following steps:
(1) adding sulfanilic acid, a phenolic compound, a viscosity reducer and water into a reaction kettle, heating to 70 ℃, stirring for dissolving, then continuously heating to a temperature not more than 80 ℃, starting to slowly dropwise add the condensing agent, completing dropwise addition within 2 hours, simultaneously keeping the temperature at 80-90 ℃, and preserving heat for 1-2 hours after dropwise addition; the phenolic compound is at least one of phenol, bisphenol A, bisphenol S, paracresol, metacresol and resorcinol; the structural formula of the viscosity reducer is
Wherein n = 5-30; the condensing agent is one or two of formaldehyde, acetaldehyde and furfural;
(2) adding an alkaline regulator into the material obtained in the step (1) to regulate the pH value to 9-10, and continuing to react for 1.5-2.5 h;
(3) adding a reaction terminator and water into the material obtained in the step (2), continuously heating to 80-90 ℃, and then preserving heat for 1.5-2.5 h;
(4) cooling the material obtained in the step (3) to room temperature, and adjusting the pH value to 7-8 to obtain the material;
the mass ratio of the sulfanilic acid to the phenolic compound to the viscosity reducer to the water to the condensing agent is 35-60: 30-70: 5-30: 200: 50-90.
2. The method of claim 1, wherein: the alkaline regulator is sodium hydroxide and/or potassium hydroxide.
3. The method of claim 1, wherein: the reaction terminator is at least one of sodium bisulfite, sodium metabisulfite and sodium sulfite.
4. The method of claim 1, wherein: in the step (3), the mass ratio of the reaction terminator to the water is 8-12: 30.
5. The method of claim 1, wherein: in the step (1), the mass ratio of the sulfanilic acid, the phenolic compound, the viscosity reducer, the water and the condensing agent is 35-55: 30-67: 6-28: 200: 52-85.
6. The method of claim 5, wherein: in the step (1), the mass ratio of the sulfanilic acid, the phenolic compound, the viscosity reducer, the water and the condensing agent is 40-55: 35-67: 6-25: 200: 52-80.
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| US5879445A (en) * | 1992-10-12 | 1999-03-09 | Chryso (S.A.) | Thinners for aqueous suspensions of mineral particles and hydraulic binder pastes |
| CN106467604A (en) * | 2016-10-14 | 2017-03-01 | 科之杰新材料集团有限公司 | A kind of viscosity reduction type polycarboxylate water-reducer and preparation method thereof |
| CN107501479A (en) * | 2017-08-16 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
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