CN111378109B - Anilino polyether, preparation method thereof and application of modified aliphatic high-efficiency water reducer - Google Patents
Anilino polyether, preparation method thereof and application of modified aliphatic high-efficiency water reducer Download PDFInfo
- Publication number
- CN111378109B CN111378109B CN201811651570.1A CN201811651570A CN111378109B CN 111378109 B CN111378109 B CN 111378109B CN 201811651570 A CN201811651570 A CN 201811651570A CN 111378109 B CN111378109 B CN 111378109B
- Authority
- CN
- China
- Prior art keywords
- polyether
- water reducer
- modified aliphatic
- water
- formaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/2627—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 nitrogen containing amine groups containing aromatic or arylaliphatic amine groups
-
- 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
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/166—Macromolecular compounds comprising sulfonate or sulfate groups obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/06—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyethers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses anilino polyether, a preparation method thereof and application of a modified aliphatic high-efficiency water reducer. The anilino polyether is prepared by substituting amino hydrogen in aniline, methylaniline and/or p-methylaniline by polyether chain segments, wherein the polyether chain segments are polyether chain segments obtained by ring-opening polymerization of ethylene oxide and/or propylene oxide. The anilino polyether can be used for synthesizing a modified aliphatic high-efficiency water reducer. Compared with the traditional aliphatic water reducer, the modified aliphatic high-efficiency water reducer has excellent water reducing performance, can effectively reduce the mixing amount of the water reducer and improve the water reducing rate.
Description
Technical Field
The invention relates to anilino polyether, a preparation method thereof and application of a modified aliphatic high-efficiency water reducer, belonging to the technical field of concrete additives
Technical Field
Concrete is widely applied to various fields as a building material, and the rapid development of concrete admixture technology is promoted along with the development of concrete, and the concrete admixture is one of indispensable components in modern concrete and is an important method and technology for modifying the concrete. The water reducing agent can greatly reduce the mixing water consumption of concrete without affecting the workability of the concrete, and has a certain contribution to the strength of the concrete member at the later stage, and the water reducing agent becomes a fifth component of the concrete after cement, sand, stones and water. The water reducer is doped into the concrete, so that the flocculation structure of cement particles in cement paste can be damaged, free water in the flocculation structure is released, the dispersion effect is achieved, and the workability of the concrete is improved.
So far, the development of concrete admixtures has undergone three generations. The first generation is the lignosulfonate common water reducer, which mainly takes cellulose in papermaking waste liquid as raw material. The second-generation water reducer is a water reducer represented by naphthalene-based superplasticizer taking beta-naphthalene sulfonic acid formaldehyde condensate as a main component, and comprises melamine-based, sulfamic acid-based, corrinone-based and aliphatic superplasticizers. The third-generation water reducer is a polycarboxylic acid high-efficiency water reducer. The dispersion mechanism of the water reducer mainly comprises two aspects: after the electrostatic repulsive force and the water reducing agent are doped into the fresh concrete, molecules of the water reducing agent are adsorbed on the surfaces of cement particles in a directional manner, so that cement particles are provided with the same charges, the same charges are mutually repelled, a cement-water system is in a relatively stable state under the action of the electric repulsive force, a flocculation structure is not easy to form, and the fluidity of the fresh concrete is increased; the steric hindrance effect, solvated long chain forms sufficient thickness on the cement particle surface, plays a role in protecting, when the cement particles with the surface adsorbed with the graft copolymer are close to each other, the long chain in the protective layer is compressed, and at the moment, the cement particles are sprung out and cannot be accessed, so that the steric hindrance effect is exerted. The dispersion effect of the first-second-generation water reducer mainly depends on electrostatic repulsion, the mixing amount of the water reducer is high, the water reducer is weak, the action mechanism of the polycarboxylate water reducer is the combined action of the electrostatic repulsion and the steric hindrance effect, the mixing amount of the water reducer is low, and the water reducer is high in water reducing rate. Compared with other water reducers, the aliphatic high-efficiency water reducer has good adaptability to cement and high cost performance, but has a series of problems such as large mixing amount, low water reducer and the like due to the limitations of the molecular structure and the dispersion mechanism of the aliphatic high-efficiency water reducer.
Aiming at the problems of the aliphatic high-efficiency water reducer, a plurality of researchers modify the aliphatic water reducer. Patent CN201110120433.7 describes a phenol modified aliphatic water reducing agent and a preparation method thereof, the water reducing agent has the advantages of early strength, remarkable enhancement performance, high slump retention value and small slump loss with time. The patent CN20090061188. X modifies the accelerant azodiisobutyronitrile, the active agent acrylic acid and other families into the aliphatic water reducing agent, thereby reducing the production cost and improving the water reducing rate, the fluidity, the workability and the like. The patent CN201310604506.9 introduces unsaturated monomers and cross-linking agents, improves the water reducing rate of the aliphatic water reducer, reduces the bleeding rate, and improves the cohesiveness, slump retention and adaptability. These patents do not change the aliphatic structure at all from the dispersion mechanism, so that the water reducing performance thereof cannot be effectively improved. The patent CN201210428351.3 provides a high water-reducing type modified aliphatic water reducer and a preparation method thereof, which introduces allyl alcohol polyoxyethylene ether with a long side chain, improves the steric hindrance, and ensures that the synthesized water reducer has higher water-reducing effect and better adaptability. The unsaturated polyether macromonomer cannot effectively participate in the reaction, the grafting rate is low, and the performance of the water reducer cannot be effectively improved.
The invention aims to modify the aliphatic water reducer from the molecular structure, graft polyether side chains on the main chain of the aliphatic acid salt water reducer, provide steric hindrance, change the dispersion mechanism of the aliphatic acid salt water reducer, and improve the dispersibility and slump retention.
Disclosure of Invention
The invention provides anilino polyether, a preparation method thereof and application of a modified aliphatic high-efficiency water reducer.
The anilino polyether is prepared by substituting amino hydrogen in aniline, methylaniline and/or p-methylaniline by polyether chain segments, wherein the polyether chain segments are polyether chain segments obtained by ring-opening polymerization of ethylene oxide and/or propylene oxide.
The anilino polyether has the following structure
Wherein R is 1 Is H-NH 2 -OH or alkyl of 1 to 4 carbon atoms or-NH (CH 2CH 2O) m (CHCH 3O) nR 2 ；R 2 Is H or alkyl of 1 to 4 carbon atoms; m and n are integers from 0 to 100.
The preparation method of the anilino polyether comprises the steps of adding aniline, methylaniline and/or p-methylaniline into a reaction kettle; adding sodium hydride as catalyst, removing hydrogen, vacuumizing for 10min, sequentially introducing ethylene oxide and propylene oxide with corresponding molar weights, reacting at 110-150 ℃ under 0.1-0.5Mpa, and reacting at a temperature of 30min after the introduction to obtain the anilino polyether.
The application of the anilino polyether can be used for synthesizing a modified aliphatic high-efficiency water reducer. By grafting an anilino polyether side chain on the main chain of the aliphatic water reducer molecule, the dispersion effect of the water reducer on cement particles is increased, and the slump retention is improved.
The modified aliphatic high-efficiency water reducer is prepared by performing condensation reaction on anilino polyether and formaldehyde to obtain pre-polycondensation polyether A, performing pre-polycondensation on acetone, formaldehyde and sulfurous acid to obtain prepolymer B, and performing mixing polycondensation on the prepolymer A and the prepolymer B to obtain the modified aliphatic water reducer. The modified aliphatic water reducer takes sulfonic acid groups as adsorption groups, and meanwhile, the modified aliphatic water reducer contains polyether long side chains to provide steric hindrance.
The weight average molecular weight Mw of the modified aliphatic water reducer is 5000-20000, and the solid content is 30-50% of aqueous solution.
The preparation method of the modified aliphatic high-efficiency water reducer comprises the following steps:
(4) Preparation of A material
Pre-polycondensing polyether and formaldehyde in water solution under the action of alkaline catalyst to obtain material A
(5) Preparation of material B
The material B is prepared by the reaction of acetone, formaldehyde, sodium bisulphite, sodium metabisulfite and sodium hydroxide.
(6) Mixing reaction
And adding the material A into the material B, and carrying out heat preservation reaction to obtain the modified aliphatic water reducer.
The preparation method of the material A comprises the following steps: the proportion of formaldehyde and polyether is 1:1-1:1.5, the alkaline catalyst can be aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, the reaction temperature is 80-120 ℃, the reaction time is 2-5h, water is taken as a solvent, and the mass fraction of the reactants is 30-80%.
The preparation method of the material B in the step (2) comprises the following steps: adding water, sulfonating agent and sodium hydroxide into a reaction kettle, regulating the PH to 7-10, stirring for 20min, heating to 30-50 ℃, dissolving sulfite, heating to 60-80 ℃, adding a mixture of formaldehyde and acetone, and carrying out heat preservation reaction for 0.5-1h after dripping to obtain the material B. Wherein the sulfonating agent: acetone = 0.4-1, formaldehyde: acetone=1.5-2.5. The sulfonating agent can be anhydrous sodium sulfite, heptahydrate sodium sulfite, sodium bisulfate, sodium metabisulfite and the like.
The step of the mixed reaction in the step (3) is as follows: and (3) adding the material A into the material B, regulating the pH of the solution to 10-13, reacting for 2-4 hours at 80-120 ℃, and adding water for dilution to obtain the modified aliphatic water reducer.
The invention provides an application method of the modified aliphatic water reducer as a cement-based material dispersing agent.
The modified aliphatic water reducer obtained by the invention can be used as a cement-based material dispersing agent singly or in combination with other water reducers, has excellent water reducing performance compared with the traditional aliphatic water reducer, can effectively reduce the mixing amount of the water reducer and improve the water reducing rate. When in use, the mixing amount (folding and fixing mixing amount) is 1-5 per mill of the mass of the cementing material, and the specific mixing amount is determined according to the actual engineering requirement. However, when the mixing amount is less than 1 per mill, the dispersibility is poor, the engineering requirement cannot be met, when the mixing amount exceeds 5 per mill, the cost performance is low, and segregation and bleeding can occur when the mixing amount is too high.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting the present invention. All equivalent changes or modifications made in accordance with the spirit of the invention should be construed to be within the scope of the present invention.
In the examples of the present invention, the molecular weight of the condensate was measured using a Wyatt technology corporation gel permeation chromatograph. The experimental conditions were as follows:
gel column: shodex SB806+803 two chromatographic columns are connected in series;
washing liquid: 0.1M NaNO3 solution;
mobile phase velocity: 1.0mL/min;
injection: 20uL of 0.5% aqueous solution;
a detector: shodex RI-71 type differential refractor;
standard substance: polyethylene glycol GPC standard (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,826,232).
The cement adopted is the field 525.5 R.P.II cement, the sand is the medium sand with the fineness modulus Mx=2.6, and the stone particle size is 5-20mm continuous graded broken stone. The fluidity of the cement paste was measured on a plate glass after stirring for 3 minutes with an amount of 87g of water added according to GB/T8077-2000 standard.
The concrete slump, water reducing rate and air content test is carried out according to the relevant regulations of the national standard GB/T8076-2008 concrete admixture, and the additive mixing amount is a folding and solidifying mixing amount.
Polyether synthesis
Adding an initiator, namely para-methylaniline, and a catalyst, namely sodium hydride, into a reaction kettle to react to remove hydrogen, vacuumizing for 10min, sequentially introducing ethylene oxide and propylene oxide with corresponding molar weights, reacting at 130 ℃ and 0.5Mpa, and preserving the temperature for 30min after the introduction to obtain the required polyether PE-1. The polyether PE-2 to PE-7 can be obtained by changing the ratio of the initiator to the ethylene oxide and the propylene oxide by the same method
Table 2 polyether list in examples
Example 1
Into a 250mL four-necked flask, 103.9g (0.05 mol) of polyether PE-1, 100g of water and 10g of 30% aqueous sodium hydroxide solution were charged, and the temperature was raised to 90℃in an oil bath, 4.05g (0.05 mol) of formaldehyde was added thereto, and the reaction was carried out for 2 hours to obtain a precondensate A. 50g of water, 18.9g (0.15 mol) of anhydrous sodium sulfite and sodium hydroxide are added into a 500mL four-necked flask to adjust the PH to 9, stirring is carried out for 20min, the temperature is raised to 40 ℃ at the same time, the anhydrous sodium sulfite is dissolved, then the temperature is raised to 70 ℃, formaldehyde and acetone mixture (48.6 g (0.6 mol) of formaldehyde and 17.4g (0.3 mol) of acetone) are added, and after the dropwise addition, the reaction is carried out for 1h while keeping the temperature, thus obtaining a material B. And adding the material A into the material B, regulating the pH value of the solution to 10 by using sodium hydroxide, reacting for 3 hours at 100 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-1 with the molecular weight Mw= 13586.
Example 2
Into a 250mL four-necked flask, 103.8g of polyether PE-2, 150g of water and 8g of 30% potassium hydroxide aqueous solution were added, the temperature was raised to 80℃in an oil bath, 4.86g of formaldehyde was added, and the reaction was carried out for 3 hours to obtain a precondensate A. 50g of water, 20.8g of sodium bisulfite and sodium hydroxide are added into a reaction kettle to adjust the PH to 8, stirring is carried out for 20min, the temperature is raised to 40 ℃, sodium bisulfite is dissolved, then the temperature is raised to 60 ℃, formaldehyde and acetone mixture (formaldehyde 48.6g and acetone 23.2 g) are added, and the mixture is reacted for 30min after the dripping is finished, thus obtaining the material B. And (3) adding the material A into the material B, regulating the pH value of the solution to 11 by using sodium hydroxide, reacting for 2 hours at 80 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-2 with the molecular weight Mw=8837.
Example 3
Into a 250mL four-necked flask, 100.3g of polyether PE-3, 0g of water and 10g of 30% sodium carbonate aqueous solution were added, the temperature was raised to 100℃in an oil bath, 4.46g of formaldehyde was added, and the reaction was carried out for 4 hours to obtain a precondensate A. 50g of water, 57.25g of sodium sulfite heptahydrate and sodium hydroxide are added into a reaction kettle to adjust the PH to 10, stirring is carried out for 20min, the temperature is raised to 40 ℃, sodium sulfite heptahydrate is dissolved, then the temperature is raised to 70 ℃, formaldehyde and acetone mixture (60.8 g of formaldehyde and 17.4g of acetone) are added, and the mixture is reacted for 1h after dropwise addition, thus obtaining the material B. And adding the material A into the material B, regulating the pH value of the solution to 12 by using sodium hydroxide, reacting for 4 hours at 120 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-3 with the molecular weight Mw=15690.
Example 4
Into a 250mL four-necked flask, 99.7g of polyether PE-4, 80g of water and 7g of 30% potassium carbonate aqueous solution are added, the temperature is raised to 110 ℃ in an oil bath, 6.08g of formaldehyde is added, and the reaction is carried out for 5 hours, thus obtaining a precondensate A. 50g of water, 23.75g of sodium metabisulfite and sodium hydroxide are added into a reaction kettle to adjust the PH to 9, stirring is carried out for 20min, meanwhile, the temperature is raised to 40 ℃, sodium metabisulfite is dissolved, then the temperature is raised to 70 ℃, formaldehyde and acetone mixture (48.6 g of formaldehyde and 17.4g of acetone) are added, and the mixture is reacted for 50min after dropwise addition, thus obtaining the material B. And adding the material A into the material B, regulating the pH of the solution to 13 by using sodium hydroxide, reacting for 3 hours at 90 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-4 with the molecular weight Mw=6732.
Example 5
Into a 250mL four-necked flask, 103.7g of polyether PE-5, 100g of water and 5g of 30% potassium carbonate aqueous solution are added, the temperature is raised to 120 ℃ in an oil bath, 5.67g of formaldehyde is added, and the reaction is carried out for 2 hours, thus obtaining a precondensate A. 50g of water, 25.2g of anhydrous sodium sulfite and sodium hydroxide are added into a reaction kettle to adjust the PH to 8, stirring is carried out for 20min, the temperature is raised to 40 ℃, the anhydrous sodium sulfite is dissolved, then the temperature is raised to 60 ℃, formaldehyde and acetone mixture (81.1 g of formaldehyde and 29g of acetone) are added, and the mixture is reacted for 40min after the dropwise addition is finished, thus obtaining the material B. And adding the material A into the material B, regulating the pH value of the solution to 10 by using sodium hydroxide, reacting for 4 hours at 110 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-5 with the molecular weight Mw=16337.
Example 6
Into a 250mL four-necked flask, 97.1g of polyether PE-6, 130g of water and 8g of 30% sodium hydroxide aqueous solution were added, the temperature was raised to 90℃in an oil bath, 4.86g of formaldehyde was added, and the reaction was carried out for 3 hours to obtain a precondensate A. Adding 50g of water, 26g of sodium bisulfite and sodium hydroxide into a reaction kettle to adjust the PH to 10, stirring for 20min, heating to 40 ℃ at the same time, dissolving sodium bisulfite, heating to 80 ℃, adding formaldehyde and acetone mixture (40.5 g of formaldehyde and 14.5g of acetone), and carrying out heat preservation reaction for 1h after the dripping is finished to obtain the material B. And adding the material A into the material B, regulating the pH value of the solution to 11 by using sodium hydroxide, reacting for 2 hours at 100 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-6 with the molecular weight Mw=12734.
Example 7
Polyether PE-7 (78 g), water (70 g) and 30% sodium hydroxide aqueous solution (8 g) are added into a four-necked 250mL flask, the temperature is raised to 90 ℃ in an oil bath, formaldehyde (4.05 g) is added, and the reaction is carried out for 4 hours, thus obtaining a pre-polycondensate A. 50g of water, 37.8g of anhydrous sodium sulfite and sodium hydroxide are added into a reaction kettle to adjust the PH to 8, stirring is carried out for 20min, the temperature is raised to 40 ℃, the anhydrous sodium sulfite is dissolved, then the temperature is raised to 60 ℃, formaldehyde and acetone mixture (113.5 g of formaldehyde and 34.8g of acetone) are added, and the mixture is reacted for 1h after the dropwise addition, thus obtaining the material B. And adding the material A into the material B, regulating the pH value of the solution to 10 by using sodium hydroxide, reacting for 3 hours at 100 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-7 with the molecular weight Mw=18835.
Example 8
Into a 250mL four-necked flask, 103.2g of polyether PE-1, 80g of water and 5g of 30% sodium hydroxide aqueous solution were added, the temperature was raised to 90℃in an oil bath, 6.08g of formaldehyde was added, and the reaction was carried out for 2 hours to obtain a precondensate A. 50g of water, 37.8g of anhydrous sodium bisulfite and sodium hydroxide are added into a reaction kettle to adjust the PH to 9, stirring is carried out for 20min, the temperature is raised to 40 ℃, the anhydrous sodium sulfite is dissolved, then the temperature is raised to 70 ℃, formaldehyde and acetone mixture (113.5 g of formaldehyde and 34.8g of acetone) are added, and the mixture is reacted for 1h after the dropwise addition is finished, thus obtaining the material B. And adding the material A into the material B, regulating the pH value of the solution to 11 by using sodium hydroxide, reacting for 3 hours at 90 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-8 with the molecular weight Mw=13732.
Example 9
Polyether PE-7 (78 g), water (70 g) and 30% sodium hydroxide aqueous solution (5 g) are added into a four-necked 250mL flask, the temperature is raised to 90 ℃ in an oil bath, formaldehyde (4.86 g) is added, and the reaction is carried out for 3 hours to obtain a pre-polycondensate A. 50g of water, 41.6g of anhydrous sodium sulfite and sodium hydroxide are added into a reaction kettle to adjust the PH to 8, stirring is carried out for 20min, the temperature is raised to 40 ℃, the anhydrous sodium sulfite is dissolved, then the temperature is raised to 60 ℃, formaldehyde and acetone mixture (102.15 g of formaldehyde and 34.8g of acetone) are added, and the mixture is reacted for 40min after the dropwise addition, thus obtaining the material B. And adding the material A into the material B, regulating the pH value of the solution to 10 by using sodium hydroxide, reacting for 2 hours at 110 ℃, and adding water for dilution to obtain the polyether modified aliphatic water reducer S-9 with the molecular weight Mw=5762.
Example 10
50g of water, 18.9g of anhydrous sodium bisulfite and sodium hydroxide are added into a reaction kettle to adjust the PH to 9, stirring is carried out for 20min, the temperature is raised to 40 ℃, the anhydrous sodium bisulfite is dissolved, then the temperature is raised to 70 ℃, formaldehyde and acetone mixture (formaldehyde 48.6g and acetone 17.4 g) is added, the reaction is carried out for 3h after the dripping is finished, and the aliphatic water reducer S-10 with the molecular weight Mw=3272 is obtained after the dilution by adding water.
Application example 1
In order to evaluate the dispersion performance of the polyether modified aliphatic water reducer to cement paste, according to the relevant regulations of the national standard GB/T8077-2000 'method for testing homogeneity of concrete admixture', 300g of cement, 87g of water and 0.3% of comparative example C-10, and 0.25% of other additives are taken, in order to examine the sensitivity of the water reducer to the amounts, C-1 and C-10 select comparative tests with different amounts, and the fluidity of paste on plate glass is tested after stirring for 3min, and the fluidity of paste after 1h is tested. The test results are shown in tables 2 and 3.
Table 1 cement paste fluidity evaluation table
TABLE 2 comparison of the flow of the slurries with different amounts of addition
As can be seen from the fluidity of the clear slurry in Table 1, the dispersibility of the polyether modified aliphatic high-efficiency water reducer prepared by the invention is greatly improved compared with that of an unmodified aliphatic water reducer (S-10), and the fluidity is basically not lost after 1 hour, and the main reason is that after polyether molecules are grafted to side chains of the aliphatic water reducer molecules, steric hindrance is formed, and the action mechanism of the water reducer on cement dispersion is changed, so that the dispersibility and slump retention of the aliphatic water reducer are improved basically. From Table 2, it can be seen that the polyether-modified aliphatic superplasticizer (S-1) has good fluidity in the blending amount (0.2% -0.35%), is insensitive to the blending amount, but bleeding occurs when the blending amount is increased continuously. The unmodified aliphatic water reducer (S-10) is sensitive to the doping amount, and the fluidity loss is fast.
Application example 2
According to the test method of the high-performance water reducer in the standard of the national standard GB8076-2008 concrete admixture, the adopted cements are the field 525.5 R.P.II cements, the sand is middle sand with fineness modulus Mx=2.6, the stones are small stones with the grain size of 5-10mm and large stones with the grain size of 10-20mm, continuous graded broken stones are used as materials, and indexes such as water reducing rate, air content, slump retention capacity and the like of the polycondensate water reducer are tested according to the ratio specified in the table 3, and the test results are shown in the table 4. The blending amount of the examples was 0.23%, and the blending amount of the comparative example S-10 was 0.3% of the cement amount.
TABLE 3 concrete mix for testing
Table 4 table for evaluating the properties of the concrete
The concrete fluidity data in Table 4 shows that the polyether modified aliphatic high-efficiency water reducer can show good dispersibility and slump retention under the condition that the doping amount is 0.23% due to the introduction of polyether side chains to provide larger steric hindrance.
Claims (6)
1. The modified aliphatic high-efficiency water reducer is characterized in that anilino polyether is utilized to synthesize the modified aliphatic high-efficiency water reducer;
the anilino polyether is a polyether segment obtained by ring-opening polymerization of epoxy ethane and/or epoxy propane, wherein the amino hydrogen in aniline, methylaniline and/or p-methylaniline is replaced by the polyether segment;
the modified aliphatic high-efficiency water reducer is prepared by performing condensation reaction on anilino polyether and formaldehyde to obtain pre-polycondensation polyether A, performing pre-polycondensation on acetone, formaldehyde and sulfurous acid to obtain prepolymer B, and performing mixing polycondensation on the prepolymer A and the prepolymer B to obtain the modified aliphatic water reducer; the anilino polyether has the following structure:
wherein R is 1 Is H, -NH 2 -OH or alkyl of 1 to 4 carbon atoms or
-NH(CH 2 CH 2 O) m (CHCH 3 O) n R 2 ；R 2 Is H or alkyl of 1 to 4 carbon atoms; m and n are integers from 0 to 100.
2. The modified aliphatic high-efficiency water reducer according to claim 1, wherein aniline, methylaniline and/or p-methylaniline are added into a reaction kettle; adding sodium hydride as catalyst, removing hydrogen, vacuumizing for 10min, sequentially introducing ethylene oxide and propylene oxide with corresponding molar weights, reacting at 110-150 ℃ and 0.1-0.5MPa, and preserving heat for 30min after the introduction to obtain the anilino polyether.
3. The modified aliphatic water reducing agent according to claim 1, wherein the weight average molecular weight Mw of the modified aliphatic water reducing agent is 5000 to 20000, and is an aqueous solution having a solid content of 30% to 50%.
4. The method for preparing the modified aliphatic high-efficiency water reducer as claimed in claim 1, which is characterized by comprising the following steps:
(1) Preparation of A material
Pre-condensing anilino polyether and formaldehyde in an aqueous solution under the action of an alkaline catalyst to obtain a material A;
(2) Preparation of material B
Preparing a material B by the reaction of acetone, formaldehyde, sodium bisulphite, sodium metabisulfite and sodium hydroxide;
(3) Mixing reaction
Adding the material A into the material B, and carrying out heat preservation reaction to obtain a modified aliphatic water reducer;
the preparation method of the material A in the step (1) comprises the following steps: the proportion of formaldehyde to polyether is 1:1-1:1.5, the alkaline catalyst is aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, the reaction temperature is 80-120 ℃, the reaction time is 2-5h, water is taken as solvent, and the mass fraction of the reactants is 30-80%;
the preparation method of the material B in the step (2) comprises the following steps: adding water, sulfonating agent and sodium hydroxide into a reaction kettle, regulating the pH to 7-10, stirring for 20min, heating to 30-50 ℃, dissolving sulfite, heating to 60-80 ℃, adding a mixture of formaldehyde and acetone, and carrying out heat preservation reaction for 0.5-1h after dripping to obtain a material B; wherein the sulfonating agent: acetone = 0.4-1, formaldehyde: acetone=1.5-2.5. The sulfonating agent is anhydrous sodium sulfite, sodium sulfite heptahydrate, sodium bisulfate and sodium metabisulfite;
the step of the mixed reaction in the step (3) is as follows: and (3) adding the material A into the material B, regulating the pH value of the solution to be between 10 and 13, reacting for 2 to 4 hours at the temperature of 80 to 120 ℃, and adding water for dilution to obtain the modified aliphatic water reducer.
5. The use of the modified aliphatic high-efficiency water reducing agent according to claim 1, wherein the modified aliphatic water reducing agent is used as a cement-based material dispersant.
6. The use according to claim 5, wherein the modified aliphatic water reducer is used as a cement-based material dispersant alone or in combination with other water reducers, and the mixing amount, i.e. the fold-fixing mixing amount, is 1-5 per mill of the mass of the cementing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811651570.1A CN111378109B (en) | 2018-12-31 | 2018-12-31 | Anilino polyether, preparation method thereof and application of modified aliphatic high-efficiency water reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811651570.1A CN111378109B (en) | 2018-12-31 | 2018-12-31 | Anilino polyether, preparation method thereof and application of modified aliphatic high-efficiency water reducer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111378109A CN111378109A (en) | 2020-07-07 |
| CN111378109B true CN111378109B (en) | 2023-05-30 |
Family
ID=71214928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811651570.1A Active CN111378109B (en) | 2018-12-31 | 2018-12-31 | Anilino polyether, preparation method thereof and application of modified aliphatic high-efficiency water reducer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111378109B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2245554A1 (en) * | 1972-09-16 | 1974-03-28 | Bayer Ag | Primary or secondary polyether amines prodn - by alkoxylation of benzyl-amines and catalytic hydrogenation, for pure colourless prod in high yield |
| CN101293757B (en) * | 2008-06-17 | 2012-04-04 | 武汉理工大学 | Polyether modification type sulfamate water reducing agent and preparation method |
| CN104230204B (en) * | 2014-09-22 | 2016-01-20 | 河南科之杰新材料有限公司 | A kind of preparation method of collapse protection type aliphatic water reducing agent |
| CN105642184B (en) * | 2014-12-02 | 2018-05-04 | 中国科学院宁波材料技术与工程研究所 | Graphene dispersion agent and its application |
| CN105399943A (en) * | 2015-12-31 | 2016-03-16 | 江苏苏博特新材料股份有限公司 | Preparation method and application of anti-soil polymer |
| CN105646871A (en) * | 2015-12-31 | 2016-06-08 | 江苏苏博特新材料股份有限公司 | Preparation method of polymer and application thereof |
| CN108250447B (en) * | 2016-12-28 | 2020-12-29 | 江苏苏博特新材料股份有限公司 | Polyether modified sulfamate high-efficiency water reducing agent, and preparation method and application thereof |
| CN109053966A (en) * | 2018-05-25 | 2018-12-21 | 湖北工业大学 | 2200 molecular weight polyether polycarboxylate water-reducers of one kind and preparation method |
| CN109970921B (en) * | 2018-06-08 | 2020-07-03 | 科之杰新材料集团有限公司 | High-water-reduction low-sensitivity polycarboxylate superplasticizer and preparation method thereof |
-
2018
- 2018-12-31 CN CN201811651570.1A patent/CN111378109B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111378109A (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10647803B2 (en) | Method for preparing concrete superplasticizer having phosphorous acid group and use thereof | |
| CN111377642B (en) | Multi-element adsorption polycarboxylate superplasticizer and preparation method and application thereof | |
| EP3398916B1 (en) | Phosphorylated polycondensate as high efficiency water reducing agent and preparation method thereof | |
| CN107337766B (en) | High-adaptability polycarboxylate superplasticizer and preparation method thereof | |
| EP1767555B1 (en) | Novel polymer and cement admixture using the same | |
| KR910006893B1 (en) | Cement dispersion agents method of producing same and method of providing fluidizing property to hydraulic cement compositions using same | |
| CN1318344C (en) | Cement admixture and cement compsn. | |
| US20210163355A1 (en) | High-adaptability viscosity-reducing polycarboxylic acid water reducer, preparation method therefor and use thereof | |
| CN108129625B (en) | Phosphonic acid-based water reducing agent, and preparation method and application thereof | |
| CN101050081A (en) | High performance water reducing agent in new type comb shaped molecular structure | |
| CN108250447B (en) | Polyether modified sulfamate high-efficiency water reducing agent, and preparation method and application thereof | |
| JP2008239416A (en) | Cement admixture | |
| CN107601945B (en) | Preparation method of carboxyl-containing modified chitin bio-based retarding superplasticizer | |
| CN112876619A (en) | Anti-mud polycarboxylate superplasticizer and preparation method thereof | |
| CN111363147A (en) | Modified polyaspartic acid reduction type water reducer and preparation method thereof | |
| CN111378109B (en) | Anilino polyether, preparation method thereof and application of modified aliphatic high-efficiency water reducer | |
| WO1997013733A1 (en) | Lignin-based concrete admixtures | |
| CN109251269B (en) | Preparation method of modified natural chitin bio-based high-performance polycarboxylate superplasticizer | |
| CN102093522B (en) | Polycarboxylic acid, use thereof and water reducer containing same | |
| CN111377645B (en) | Micromolecular phosphonic acid water reducing agent suitable for machine-made sand and preparation method thereof | |
| CN102206314A (en) | Polycarboxylic acid and application thereof, and cement water reducing agent containing polycarboxylic acid | |
| CN112759756B (en) | Block PEG active macromonomer, preparation method and application thereof | |
| CN115368475A (en) | Preparation method of carboxyl and sulfo modified natural cellulose high polymer retarding superplasticizer, product and application thereof | |
| CN114478943A (en) | Modified cyclodextrin grafted block polycarboxylate superplasticizer and preparation method thereof | |
| CN108264615B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |