CN111116898B - Clay inhibitor for polycarboxylate superplasticizer and preparation method thereof - Google Patents
Clay inhibitor for polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN111116898B CN111116898B CN201911294054.2A CN201911294054A CN111116898B CN 111116898 B CN111116898 B CN 111116898B CN 201911294054 A CN201911294054 A CN 201911294054A CN 111116898 B CN111116898 B CN 111116898B
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- polyethylene glycol
- monomethyl ether
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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
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
- C08G65/33358—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic aromatic
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
Abstract
The invention discloses a clay inhibitor for a polycarboxylate water reducer and a preparation method thereof, wherein polyethylene glycol monomethyl ether is heated to be completely molten, toluene accounting for 10-15% of the mass of the polyethylene glycol monomethyl ether is added for refluxing and carrying water, and after no water is carried out, the residual toluene is distilled out by reduced pressure distillation; adding 2, 4-toluene diisocyanate into the dehydrated polyethylene glycol monomethyl ether under stirring, and reacting for 2-3 hours under stirring at 70-80 ℃ after the addition is finished; and (2-aminoethyl) trimethyl ammonium chloride hydrochloride and sodium hydroxide are dissolved in water in sequence, the obtained water solution is cooled to 0-5 ℃, then the water solution is added into the product obtained in the previous step under stirring, and after the addition is finished, the reaction is carried out for 1-2 hours under stirring at room temperature, so that the catalyst is obtained. The clay inhibitor can be rapidly adsorbed on the surface of clay through electrostatic action and can be inserted into montmorillonite layers, so that adsorption and intercalation behaviors of the polycarboxylate superplasticizer on the surface and the layers of the clay can be well inhibited, and the influence of the clay on the dispersibility of the polycarboxylate superplasticizer is greatly reduced.
Description
Technical Field
The invention relates to a clay inhibitor compounded with a polycarboxylic acid water reducing agent and a preparation method thereof, belonging to the field of concrete admixtures.
Background
The polycarboxylate superplasticizer is a comb-shaped water-soluble polymer consisting of a main chain rich in carboxylic acid and sulfonic acid groups and a polyoxyethylene side chain, has the advantages of adjustable molecular structure, low mixing amount, high water-reducing rate and the like, and is widely applied to various concrete projects. With the rapid development of the building industry in China, the consumption of the sandstone is high, the high-quality sandstone resource is increasingly reduced, and the sandstone with high mud content gradually becomes a concrete raw material. A large number of engineering practices and researches show that the water reducing and dispersing capacity of the polycarboxylate water reducer is seriously influenced by soil, particularly clay components in sand. On the one hand, the adsorption capacity and adsorption rate of the clay to the polycarboxylate superplasticizer are much higher than those of cement, so that a large number of polycarboxylate superplasticizer molecules are electrostatically adsorbed on the surface of the clay, and the number of the water reducer molecules playing a role of dispersing cement is reduced; on the other hand, polyether side chains in the polycarboxylate superplasticizer molecules are very easy to intercalate into montmorillonite layers in clay, and cannot play a steric hindrance role. The adsorption and intercalation behaviors greatly reduce the water reducing and dispersing capacity of the polycarboxylate superplasticizer, so that the slump loss of concrete is too fast, the transportation, pumping and construction requirements of the concrete are difficult to guarantee, and the adverse effect on the strength of the concrete is also generated. Therefore, the method for reducing the influence of the clay on the dispersion performance of the polycarboxylate water reducer by taking measures has important practical significance for expanding the application of the polycarboxylate water reducer.
At present, the influence of clay on the dispersion performance of a water reducing agent is reduced by adopting a method of super-doping a polycarboxylic acid water reducing agent in engineering, and the action mechanism is as follows: after the clay adsorbs the super-doped part, enough polycarboxylic acid water reducing agent molecules in the system play a dispersing role. This method not only increases the use cost, but also makes it difficult to control the amount of super-doping, and may cause problems such as initial severe segregation of concrete, excessively long setting time, and the like. At present, another method for more research is to compound a polycarboxylate superplasticizer and a clay inhibitor, and the action mechanism is as follows: compared with the polycarboxylate water reducer, the clay inhibitor can be adsorbed on the surface and the interlayer of the clay more quickly and easily, and the polycarboxylate water reducer is difficult to adsorb after the clay is adsorbed and saturated, so that the influence of the clay on the dispersibility of the water reducer is reduced. Most of the clay inhibitors reported so far are mainly small molecular quaternary ammonium salt compounds (see: CN 108545978), cationic copolymers (see: CN 103723941, CN 104151477), polyethylene glycol (see: 2016, 34(6):110-115, university of Shanxi science and technology) and their complexes (see: CN 106517866). Wherein, the small molecular quaternary ammonium salt compound and the cationic copolymer can be quickly adsorbed to the surface of the clay through electrostatic action, but the mixing amount of the small molecular quaternary ammonium salt compound and the cationic copolymer is generally required to be higher, so that the cost of the additive is increased; in addition, when they are used together with an anionic polycarboxylic acid water reducing agent, precipitates or floc suspensions are easily formed, resulting in poor compatibility. The polyethylene glycol can be inserted between montmorillonite layers to play a role in inhibiting the water absorption and expansion of montmorillonite and inhibiting the polyether side chain of the polycarboxylic acid water reducing agent from being embedded between the montmorillonite layers; however, since it is electrically neutral, it interacts weakly with the clay surface, and when it is used in combination with a polycarboxylic acid water reducing agent, it is difficult to be adsorbed more quickly and easily on the clay surface.
Disclosure of Invention
In order to solve the problem that the water reducing and dispersing capacity of a polycarboxylate water reducer is seriously influenced by soil in sand, particularly clay components, the invention prepares a clay inhibitor which is compounded with the polycarboxylate water reducer for use, so as to reduce the adsorption and intercalation of the polycarboxylate water reducer on the surface and among layers of clay.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a clay inhibitor for a polycarboxylic acid water reducing agent comprises the following steps:
(1) refluxing and dewatering: heating polyethylene glycol monomethyl ether (MPEG) until the polyethylene glycol monomethyl ether (MPEG) is completely melted, adding toluene accounting for 10-15% of the mass of the polyethylene glycol monomethyl ether (MPEG) to carry out reflux and water carrying, and carrying out reduced pressure distillation to evaporate the residual toluene after no water is carried out;
(2) and (3) isocyanate blocking: adding 2, 4-toluene diisocyanate (2,4-TDI) into the dehydrated polyethylene glycol monomethyl ether (MPEG) in the step (1) under stirring, and reacting under stirring at 70-80 ℃ for 2-3 hours after the addition is finished;
(3) end cationization: and (2-aminoethyl) trimethyl ammonium chloride hydrochloride and sodium hydroxide are dissolved in water in sequence, the obtained water solution is cooled to 0-5 ℃, then the water solution is added into the product obtained in the step (2) under stirring, and after the addition is finished, the reaction is carried out for 1-2 hours under stirring at room temperature, so that the catalyst is obtained.
Preferably, in the step (1), the molecular weight of the polyethylene glycol monomethyl ether is in the range of 1000-1500.
Specifically, in the step (1), the temperature of the reduced pressure distillation is 55-70 ℃, and the pressure is 10-15 mmHg. The purpose of the reflux water removal is to remove as much water as possible from the MPEG and to avoid the reaction of 2, 4-toluene diisocyanate (2,4-TDI) with water.
Specifically, in the step (2), the molar ratio of the added amount of the 2, 4-toluene diisocyanate to the polyethylene glycol monomethyl ether is 1-1.05: 1. One isocyanate group of 2,4-TDI reacts with a terminal hydroxyl group of MPEG to introduce one isocyanate group at the molecular chain terminal of MPEG, so as to prepare for the next terminal cationization.
Specifically, in the step (3), the molar ratio of the dosage of the (2-aminoethyl) trimethyl ammonium chloride hydrochloride to the polyethylene glycol monomethyl ether is 1-1.1: 1; the molar ratio of the amount of the sodium hydroxide to the polyethylene glycol monomethyl ether is 1: 1; the mass ratio of the water to the polyethylene glycol monomethyl ether is 80: 20. After (2-aminoethyl) trimethyl ammonium chloride hydrochloride is neutralized by sodium hydroxide, the amino group of the hydrochloride further reacts with the isocyanate-terminated MPEG obtained in step (2), and quaternary ammonium salt cationic groups are introduced at the molecular chain ends of the MPEG.
Preferably, in step (2), the 2, 4-toluene diisocyanate is added over 30 minutes.
Preferably, in step (3), the addition of the aqueous solution obtained is completed within 30 minutes.
Has the advantages that:
1. the clay inhibitor prepared by the invention is a terminal cationization polyethylene glycol monomethyl ether linear oligomer, the molecular size is much smaller than that of a comb-shaped structure polycarboxylate water reducer molecule, the polycarboxylate water reducer can be rapidly adsorbed to the surface of clay through electrostatic action and can also be inserted into montmorillonite layers, so that the adsorption and intercalation behaviors of the polycarboxylate water reducer on the surface and the interlayer of the clay can be well inhibited, and the influence of the clay on the dispersibility of the polycarboxylate water reducer is greatly reduced.
2. The clay inhibitor prepared by the invention has good water solubility and good compatibility with a polycarboxylic acid water reducing agent, and cannot form precipitate or flocculent suspension when used together.
3. In the preparation method, the activity of the two-step end capping reaction is very high, so that the smooth proceeding of the end capping reaction can be ensured; moreover, the reaction condition is mild, and subsequent separation and purification are not needed.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a reaction scheme diagram for preparing a clay inhibitor for a polycarboxylate water reducer.
Detailed Description
The invention will be better understood from the following examples.
Example 1
The clay inhibitor was prepared according to the reaction scheme shown in FIG. 1.
(1) Refluxing and dewatering: heating 2 kg of polyethylene glycol monomethyl ether (MPEG, molecular weight 1000) until the polyethylene glycol monomethyl ether is completely melted, adding 0.2 kg of toluene to carry out reflux and water carrying, and distilling at 60 ℃ under reduced pressure to evaporate the residual toluene after no water is carried out;
(2) and (3) isocyanate blocking: adding the dehydrated MPEG obtained in the step (1) into 0.348 kg of 2, 4-toluene diisocyanate (2,4-TDI) under stirring for 30 minutes, and then reacting under stirring at 70 ℃ for 2 hours;
(3) end cationization: and (3) sequentially dissolving 0.35 kg of (2-aminoethyl) trimethyl ammonium chloride hydrochloride and 0.08 kg of sodium hydroxide in 8 kg of water, cooling the obtained water solution to 0-5 ℃, adding the water solution into the product obtained in the step (2) under stirring for 30 minutes, and stirring and reacting at room temperature for 1 hour after the water solution is added to obtain the clay inhibitor mother solution with the solid content of about 25%.
Example 2
(1) Refluxing and dewatering: heating 2 kg of polyethylene glycol monomethyl ether (MPEG, molecular weight 1200) until the polyethylene glycol monomethyl ether is completely melted, adding 0.24 kg of toluene to carry out reflux and water carrying, and distilling at 60 ℃ under reduced pressure to evaporate the residual toluene after no water is carried out;
(2) and (3) isocyanate blocking: adding the dehydrated MPEG of the step (1) into 0.296 kg of 2, 4-toluene diisocyanate (2,4-TDI) under stirring, completing the addition for 30 minutes, and then stirring and reacting at 75 ℃ for 2.5 hours;
(3) end cationization: and (3) sequentially dissolving 0.306 kg of (2-aminoethyl) trimethyl ammonium chloride hydrochloride and 0.07 kg of sodium hydroxide in 8 kg of water, cooling the obtained water solution to 0-5 ℃, adding the water solution into the product obtained in the step (2) under stirring, adding the water solution for 30 minutes, and stirring and reacting at room temperature for 1.5 hours after adding the water solution to obtain the clay inhibitor mother solution with the solid content of about 24%.
Example 3
(1) Refluxing and dewatering: heating 2 kg of polyethylene glycol monomethyl ether (MPEG, molecular weight 1500) until the polyethylene glycol monomethyl ether is completely melted, adding 0.3 kg of toluene to carry out reflux and water carrying, and distilling at 60 ℃ under reduced pressure to evaporate the residual toluene after no water is carried out;
(2) and (3) isocyanate blocking: adding the dehydrated MPEG of the step (1) into 0.244 kg of 2, 4-toluene diisocyanate (2,4-TDI) under stirring, completing the addition for 30 minutes, and then stirring and reacting for 3 hours at 80 ℃;
(3) end cationization: and (2) sequentially dissolving 0.257 kg of (2-aminoethyl) trimethyl ammonium chloride hydrochloride and 0.059 kg of sodium hydroxide in 8 kg of water, cooling the obtained water solution to 0-5 ℃, adding the water solution into the product obtained in the step (2) under stirring, completing the addition for 30 minutes, and stirring and reacting at room temperature for 2 hours after completing the addition to obtain the clay inhibitor mother solution with the solid content of about 23%.
Example 4
The concrete experiments are used to specifically illustrate the effect of the clay inhibitor prepared in the above 3 examples on the clay inhibition. The experimental temperature is 25 ℃, and the cement is PO42.5 cement of Jiangsu Helin cement factory: the 3-day intensity was 27.8MP, the 28-day intensity was 47.3 MP; the fly ash is Nanjing Huaneng second-grade coal ash, and the water demand ratio is measured to be 99; the sand is natural sand, and the fineness modulus of the sand is 2.5; the stones were 5-25 continuous graded and the crush value was measured to be 8. The mass ratio of cement, fly ash, sand, stone and water in the concrete is 288:72:777:1073: 176. The water reducing agent is a common polycarboxylic acid water reducing agent sold in the market, and the mixing amount of the water reducing agent and the clay inhibitor is calculated by taking the mass of the gelled material after being folded and solidified as a reference. The clay is a uniform mixture of montmorillonite and kaolin with the mass ratio of 50:50, and the addition amount of the clay accounts for 2% of the mass of the sand. The slump change with time was measured according to the test method specified in GB 8076 + 2008 "concrete Water reducing Agents", and the results are shown in Table 1.
TABLE 1
As can be seen from the experimental results of table 1: the addition of 2% of clay directly results in a great decrease in initial slump, and slump loss with time is severe. After the clay inhibitor is added, the initial slump is improved, and the slump loss is small with the passage of time. Therefore, the clay inhibitor provided by the invention shows good mud slump-resistant effect.
The invention provides a clay inhibitor for a polycarboxylate water reducer and a preparation method thereof, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should also be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (9)
1. The preparation method of the clay inhibitor for the polycarboxylate superplasticizer is characterized by comprising the following steps:
(1) refluxing and dewatering: heating polyethylene glycol monomethyl ether until the polyethylene glycol monomethyl ether is completely melted, adding toluene accounting for 10-15% of the mass of the polyethylene glycol monomethyl ether to carry out reflux and water carrying, and carrying out reduced pressure distillation to evaporate the residual toluene after no water is carried out;
(2) and (3) isocyanate blocking: adding the dehydrated polyethylene glycol monomethyl ether in the step (1) into 2, 4-toluene diisocyanate under stirring, and reacting under stirring at 70-80 ℃ for 2-3 hours after the addition is finished;
(3) end cationization: and (2-aminoethyl) trimethyl ammonium chloride hydrochloride and sodium hydroxide are dissolved in water in sequence, the obtained water solution is cooled to 0-5 ℃, then the water solution is added into the product obtained in the step (2) under stirring, and after the addition is finished, the reaction is carried out for 1-2 hours under stirring at room temperature, so that the catalyst is obtained.
2. The preparation method of the clay inhibitor for the polycarboxylate water reducer as claimed in claim 1, wherein in the step (1), the molecular weight of the polyethylene glycol monomethyl ether is 1000-1500.
3. The preparation method of the clay inhibitor for the polycarboxylate water reducer as claimed in claim 1, wherein in the step (1), the temperature of the reduced pressure distillation is 55-70 ℃ and the pressure is 10-15 mmHg.
4. The preparation method of the clay inhibitor for the polycarboxylate water reducer, according to the claim 1, characterized in that in the step (2), the molar ratio of the added amount of the 2, 4-toluene diisocyanate to the polyethylene glycol monomethyl ether is 1-1.05: 1.
5. The preparation method of the clay inhibitor for the polycarboxylate water reducer, according to the claim 1, characterized in that in the step (3), the molar ratio of the (2-aminoethyl) trimethylammonium chloride hydrochloride to the polyethylene glycol monomethyl ether is 1-1.1: 1.
6. The preparation method of the clay inhibitor for the polycarboxylate water reducer as claimed in claim 1, wherein in the step (3), the molar ratio of the amount of the sodium hydroxide to the amount of the polyethylene glycol monomethyl ether is 1: 1.
7. The preparation method of the clay inhibitor for the polycarboxylate water reducer as claimed in claim 1, wherein in the step (3), the mass ratio of the water to the polyethylene glycol monomethyl ether is 80: 20.
8. The method for preparing a clay inhibitor for a polycarboxylic acid water reducer according to claim 4, characterized in that, in the step (2), the 2, 4-toluene diisocyanate is added within 30 minutes.
9. The method for producing a clay inhibitor for a polycarboxylic acid water reducing agent according to claim 1, characterized in that, in the step (3), the addition of the obtained aqueous solution is completed within 30 minutes.
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