CN115612086B - Double-arm side chain structure monomer and preparation method thereof, and water reducing agent and preparation method thereof - Google Patents

Double-arm side chain structure monomer and preparation method thereof, and water reducing agent and preparation method thereof Download PDF

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CN115612086B
CN115612086B CN202211632916.XA CN202211632916A CN115612086B CN 115612086 B CN115612086 B CN 115612086B CN 202211632916 A CN202211632916 A CN 202211632916A CN 115612086 B CN115612086 B CN 115612086B
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arm side
double
monomer
side chain
chain structure
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CN115612086A (en
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汪咏梅
黄玉美
倪涛
宋欣
李茜茜
田献文
韩晓东
刘旭飞
石雄松
田宇
朱世亮
康静
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Sichuan Concrete Road Technology Co ltd
Shijiazhuang Chang'an Yucai Building Materials Co ltd
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Sichuan Concrete Road Technology Co ltd
Shijiazhuang Chang'an Yucai Building Materials Co ltd
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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
    • C08G65/2609—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 aliphatic hydroxyl 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
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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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  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)

Abstract

The invention provides a double-arm side chain structure monomer and a preparation method thereof, and a water reducing agent and a preparation method thereof. The water reducing agent prepared from the monomer with double-arm side chain structure can solve the problem of application defects of the traditional water reducing agent in ultra-high-strength concrete, and has the characteristics of low mixing amount and strong dispersing capacity.

Description

Double-arm side chain structure monomer and preparation method thereof, and water reducing agent and preparation method thereof
Technical Field
The invention relates to the field of concrete building materials, in particular to a double-arm side chain structure monomer and a preparation method thereof, and also relates to a water reducing agent prepared by the double-arm side chain structure monomer and a preparation method thereof.
Background
With the contradictory activation of energy crisis and resource shortage, the concept of green and low-carbon development of building materials is further strengthened; the crisis of the durability of common concrete is increasingly appearing; and the advance of modern buildings to high-rise, large-span and light-weight, the research and application of ultra-high-strength and high-performance concrete (more than or equal to 100 MPa) will become the inevitable trend of future development. As is well known, the current technical means for preparing the ultra-high-strength concrete mainly adopts high-strength coarse aggregate, uses high-strength cement, increases the using amount of cementing materials, reduces the water-cement ratio to increase the strength of the concrete, and reduces the cracking risk of the concrete by doping a large amount of mineral admixtures.
Due to the adoption of the means, compared with common concrete, the combined water consumption of a concrete system is greatly increased, the free water content is greatly reduced, and great challenge is brought to concrete admixtures. Under the condition of ultralow water-to-gel ratio, the conventional water reducing agent has seriously insufficient dispersing capacity, the defect can be overcome only by greatly increasing the using amount of the water reducing agent, the increase of the using amount of the water reducing agent causes the large increase of free water reducing agent molecules in slurry, the molecules are seriously wound, the frost is caused on snow of the ultrahigh-strength concrete with the viscosity problem, and the urgent need exists on how to improve the dispersing capacity of the water reducing agent in the ultrahigh-strength concrete.
Disclosure of Invention
In view of the above, the invention provides a double-arm side chain structure monomer for preparing a water reducing agent, and the water reducing agent prepared by using the double-arm side chain structure monomer can improve the dispersing capacity of the water reducing agent in ultra-high-strength concrete.
In order to achieve the above purpose, the technical scheme of the invention is realized in such a way.
A double-arm side chain structure monomer has a molecular formula as follows:
Figure 499096DEST_PATH_IMAGE001
；
in the above formula, n is more than or equal to 1 and less than or equal to 5, a is more than 90, b is more than 90 1
Figure DEST_PATH_IMAGE002
= or
Figure 719993DEST_PATH_IMAGE003
，R 2 =
Figure 73614DEST_PATH_IMAGE002
Or
Figure 75068DEST_PATH_IMAGE004
。
Further, the molecular weight of the double-arm side chain structural monomer is 5000-8000.
Further, the molar amount of the ethoxy groups of the double-arm side chain structural monomer accounts for more than 70% of the total molar amount of the ethoxy groups and the propoxy groups.
The end of the monomer with double-arm side chain structure has an unsaturated bond, and can be polymerized with unsaturated acid to form a polymer with the function of dispersing cement. Flexible 1, 2-ethylenedioxy groups followed by unsaturated bonds, and also rigid polyalkyl ether structures, and polyether long-side arms. When the monomer with double-arm side chain structure is polymerized with unsaturated acid, water reducing agent molecules with the function of dispersing cement particles are formed, and the flexible front section of the water reducing agent molecules is favorable for improving the freedom degree of the polyether long side chain in motion in a liquid phase, so that the timeliness of the steric hindrance effect of the polyether long side chain is improved. Secondly, the polyether chain EO-PO hybrid rigid structure is not easy to wind, and the steric hindrance effect can be better enhanced and stabilized. And the double-arm structure of the water reducing agent can greatly improve the steric effect of the water reducing agent. The water reducing agent prepared from the monomer with double-arm side chain structure can solve the problem of application defects of the traditional water reducing agent in ultra-high strength concrete, and has the characteristics of low mixing amount and strong dispersing ability.
The invention also provides a preparation method of the monomer with double-arm side chain structure, which comprises the following steps:
mixing vinyl glycol ether, a catalyst and an alkaline compound, stirring for dissolving, then dropwise adding halogenated alkyl alcohol, heating, keeping the temperature, cooling to room temperature, washing with water and drying to obtain hydroxyl-terminated alkyl ether; mixing the hydroxyl-terminated alkyl ether and an alkaline compound, stirring and heating, dripping glycidol, preserving heat, cooling to room temperature, and filtering to obtain unsaturated glycol ether; and mixing the unsaturated glycol ether and an alkaline compound, stirring and heating, introducing ethylene oxide and/or propylene oxide, and cooling after the reaction is finished to obtain the double-arm side chain structure monomer.
Further, the catalyst comprises an alkali metal halide; and/or the alkaline compound comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide and sodium ethoxide; and/or, the halogenated alkyl alcohol comprises at least one of chlorohydrin, chloropropanol, chlorobutanol, chloropentanol, chlorohexanol, bromoethanol, bromopropanol, bromobutanol, bromopentanol and bromohexanol.
Further, the molar ratio of the vinyl glycol ether to the halogenated alkyl alcohol is 1.05-1.1.
Further, the molar ratio of the hydroxyl-terminated alkyl ether to the glycidol is 1.2 to 1.3.
The invention further provides a water reducing agent, wherein the preparation raw materials of the water reducing agent comprise the monomer with double-arm side chain structure and unsaturated acid, and the molar ratio of the monomer with double-arm side chain structure to the unsaturated acid is 1.5-5.
The invention also provides a preparation method of the water reducing agent, which comprises the following steps:
mixing the aqueous solution of the monomer with the double-arm side chain structure with the aqueous solution of an oxidant, then dropwise adding the solution A and the solution B, and obtaining the water reducer after the reaction is finished; the solution A is an aqueous solution of unsaturated acid, and the solution B is an aqueous solution of reducing agent and chain transfer agent.
Further, the unsaturated acid comprises at least one of acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid, acrylamide and sodium styrene sulfonate; and/or the reducing agent comprises at least one of vitamin C, ferrous sulfate and sodium hypophosphite; and/or the oxidant comprises at least one of hydrogen peroxide, ammonium persulfate and potassium persulfate; and/or, the chain transfer agent comprises at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, and sodium methallylsulfonate.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. In addition, except for the specific description of the present embodiment, the terms and processes referred to in the present embodiment should be understood according to the common knowledge and conventional methods in the prior art.
A double-arm side chain structure monomer has a molecular formula as follows:
Figure 195340DEST_PATH_IMAGE001
；
in the above formula, n is more than or equal to 1 and less than or equal to 5, a is more than 90, b is more than 90 1 =
Figure 598639DEST_PATH_IMAGE002
Or
Figure 388741DEST_PATH_IMAGE005
，R 2 =
Figure 877491DEST_PATH_IMAGE002
Or
Figure 286607DEST_PATH_IMAGE006
。
The end of the monomer with double-arm side chain structure has an unsaturated bond, and can be polymerized with unsaturated acid to form a polymer with the function of dispersing cement. Flexible 1, 2-ethylenedioxy groups followed by unsaturated bonds, and also rigid polyalkyl ether structures, and polyether long-side arms. When the monomer with double-arm side chain structure is polymerized with unsaturated acid, water reducing agent molecules capable of dispersing cement particles are formed, and the flexible front section of the water reducing agent molecules is favorable for improving the freedom degree of movement of the polyether long side chain in a liquid phase, so that the timeliness of the steric hindrance effect of the polyether long side chain is improved. Secondly, the polyether chain is
Figure 341150DEST_PATH_IMAGE002
And
Figure 505415DEST_PATH_IMAGE007
the hybridized rigid structure is not easy to wind, and the steric hindrance effect can be better enhanced and stabilized. And the double-arm structure of the water reducing agent can greatly improve the steric effect of the water reducing agent. It should be noted that the groups represented by R1 and R2 on the polyether chains of the above formula are random in the two possible ranges, since the intermediates of the preparation process are random when ethylene oxide and propylene oxide are grafted. The water reducing agent prepared by the monomer with double-arm side chain structure can improve the application of the traditional water reducing agent in ultra-high-strength concreteDefect problem, low mixing amount and strong dispersing ability.
The molecular weight of the monomer with double-arm side chain structure is adjusted according to the polymerization degree of double arms, the preferable molecular weight of the monomer with double-arm side chain structure is 5000-8000, so that the water reducing agent prepared from the monomer has long side chains, and the long side chains are not too long and are easy to tangle. Further, the mole ratio of the ethoxy group in the long side chain of the monomer with double-arm side chain structure to the total mole ratio of ethoxy group to propoxy group is more than 70%, so that the water solubility is better.
The invention also provides a preparation method of the monomer with double-arm side chain structure, which comprises the following steps:
adding vinyl glycol ether, a catalyst and a solid alkaline compound into a three-neck flask provided with a reflux condenser tube and a thermometer, mixing, heating to 45 ℃, stirring for dissolving, then dropwise adding halogenated alkyl alcohol, heating to 60-80 ℃, reacting for 2-4h under heat preservation, cooling to room temperature, washing with water and drying to obtain the hydroxyl-terminated alkyl ether. The reaction formula is as follows:
Figure 668412DEST_PATH_IMAGE008
x in the reaction formula is a halogen element, such as chlorine and bromine. The catalyst of this step preferably comprises an alkali metal halide, such as at least one of sodium chloride, potassium chloride, sodium bromide, and potassium bromide. The alkali compound is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, and sodium ethoxide. The alkyl halide preferably includes at least one of chloroethanol, chloropropanol, chlorobutanol, chloropentanol, chlorohexanol, bromoethanol, bromopropanol, bromobutanol, bromopentanol and bromohexanol. The molar ratio of vinyl glycol ether to the halogenated alkyl alcohol in this step is preferably 1.05 to 1.1. The molar ratio of vinyl glycol ether to basic compound is preferably 1.1 to 1.2. The mass ratio of the catalyst to the raw materials is preferably 5-10%.
Then mixing an alkaline compound with the hydroxyl-terminated alkyl ether, adding the mixture into a three-neck flask provided with a reflux condenser tube and a thermometer, stirring and heating the mixture to 50-70 ℃, dropwise adding glycidol under stirring, keeping the temperature for 2-3h, cooling the mixture to room temperature, and filtering the mixture to obtain unsaturated glycol ether. The preferred molar ratio of the hydroxyl-terminated alkyl ether to the glycidol in this step is 1.2 to 1.3. The molar ratio of the hydroxyl-terminated alkyl ether to the basic compound is 1.05 to 1.2. The reaction formula is as follows:
Figure 677957DEST_PATH_IMAGE009
and then mixing the unsaturated glycol ether and an alkaline compound, stirring and heating to 80-100 ℃, introducing ethylene oxide and/or propylene oxide, reacting for 4-6h, and cooling to obtain the double-arm side chain structure monomer. The preferable mol ratio of the unsaturated glycol ether to the alkaline compound in the step is 1.2-2.3, and the mol ratio of the unsaturated glycol ether to the alkylene oxide is 1: 60-140. The preferred molar ratio of ethylene oxide to the alkylene oxide is greater than 60% to provide better water solubility of the prepared monomers with double-arm side chain structures. The epoxy groups of the ethylene oxide and the propylene oxide are opened and are subjected to dehydration, etherification and condensation with two hydroxyl groups at the ends of the unsaturated glycol ether to form a polyether double-arm side chain structure.
The invention further provides a water reducing agent, which is prepared by mixing the double-arm side chain structure monomer and unsaturated acid according to the molar ratio of 1.5-5 and then initiating polymerization through an oxidation-reduction system.
The water reducing agent adopts the monomer with the double-arm side chain structure to polymerize with unsaturated acid to form comb-shaped water reducing agent molecules, carboxylic acid groups provided by the unsaturated acid on the main chain of the polymer molecules of the water reducing agent can be adsorbed with metal ions on the surfaces of cement particles, so that the polymer molecules are anchored on the surfaces of the cement particles, negative charges are carried on the surfaces of the cement particles to form an electrostatic repulsion effect, the cement particles are promoted to be mutually dispersed, a flocculation structure is disintegrated, wrapped water is released to participate in flowing, and the fluidity of concrete mixtures is effectively increased. The side chains are high molecular weight polyether provided by double-arm side chain structural monomers, long side chains of the polyether are spread out, a steric hindrance effect is generated among cement particles, coagulation among the cement particles is hindered, and the cement particles are dispersed. The water reducing agent prepared from the double-arm side chain structure monomer can solve the problem of application defects of the traditional water reducing agent in ultra-high strength concrete, and has the characteristics of low mixing amount and strong dispersing capacity.
The invention also provides a preparation method of the water reducing agent, which comprises the following steps:
the aqueous solution of the double-arm side chain structural monomer and the aqueous solution of the oxidant are mixed in a three-neck flask provided with a thermometer. And preparing materials A and B, wherein A is an aqueous solution of unsaturated acid, and B is an aqueous solution mixed by a reducing agent and/or a chain transfer agent, heating a three-neck flask to 10-35 ℃, stirring for 5min, then starting dropwise adding the materials A and B, keeping the temperature after dropwise adding is finished, and adding dilution water after the reaction is finished to finally obtain the water reducing agent with the solid content of 40%. The amount of the oxidant and the reducer accounts for 0.1-1.5% of the mass of the monomer, and the amount of the chain transfer agent accounts for 0.2-1% of the mass of the monomer.
Specific embodiments of the present invention are described in detail below.
Example 1
Adding 88g of vinyl glycol ether, 1.1g of sodium bromide and 44g of sodium hydroxide solid into a three-neck flask provided with a reflux condenser tube and a thermometer, stirring and heating to 45 ℃, adding 115g of bromobutanol dropwise under stirring until the sodium bromide solid is completely dissolved, heating to 70 ℃, reacting for 2.5h, cooling to room temperature, neutralizing, washing with water and drying to obtain the hydroxyl-terminated alkyl ether.
144g of the hydroxyl-terminated alkyl ether and 46g of sodium hydroxide solid are added into a three-neck flask provided with a reflux condenser tube and a thermometer, the temperature is raised to 50 ℃ by stirring, 60g of glycidol is added dropwise to react for 2 hours by stirring, the mixture is cooled to room temperature, and the unsaturated glycol ether is obtained by filtration.
218g of the unsaturated glycol ether obtained above and 53g of sodium hydride solid are added into a flask provided with a reflux condenser and a thermometer, the temperature is raised to 90 ℃ by stirring, 2520g of ethylene oxide and 1134g of propylene oxide are introduced under stirring, the mixture reacts for 5 hours, and the monomer with the double-arm side chain structure is obtained by cooling.
In a three-necked flask equipped with a thermometer, 100g of the above-mentioned two-arm side chain structural monomer and 60g of deionized water were charged. A material A and a material B are prepared simultaneously, wherein the material A comprises 5.76g of acrylic acid and 20g of deionized water, and the material B comprises 0.3g of mercaptopropionic acid, 0.15g of vitamin C and 50g of deionized water. And (3) heating the three-neck flask to 20 ℃, adding 0.9g of hydrogen peroxide, stirring for 5min, then beginning to dropwise add the materials A and B, respectively dripping for 40min and 50min, preserving the temperature for 60min, and adding dilution water after the reaction is finished to finally obtain the 40% solid water reducer with the double-arm side chain structure.
Example 2
Adding 88g of vinyl glycol ether, 1.08g of potassium chloride and 60g of potassium hydroxide solid into a three-neck flask provided with a reflux condenser tube and a thermometer, stirring and heating to 50 ℃, adding 86g of chloropropanol dropwise under stirring until the vinyl glycol ether is completely dissolved, heating to 75 ℃, reacting for 3 hours, cooling to room temperature, neutralizing, washing with water and drying to obtain the hydroxyl-terminated alkyl ether.
129g of the obtained hydroxyl-terminated alkyl ether and 60g of potassium hydroxide solid are added into a three-neck flask provided with a reflux condenser tube and a thermometer, stirred and heated to 50 ℃, 58g of glycidol is added dropwise to react for 2.5h under stirring, cooled to room temperature, and filtered to obtain unsaturated glycol ether.
203g of the unsaturated glycol ether obtained above and 84g of potassium hydride solid are added into a flask provided with a reflux condenser and a thermometer, the temperature is raised to 80 ℃ by stirring, 3386g of ethylene oxide and 1872g of propylene oxide are introduced under stirring, the reaction is carried out for 6h, and the monomer with the double-arm side chain structure is obtained by cooling.
120g of the above-mentioned double-arm side chain structural monomer, 1.96g of maleic anhydride, and 80g of deionized water were placed in a three-necked flask equipped with a thermometer. Preparing materials A and B at the same time, wherein the material A comprises 4.32g of acrylic acid and 20g of deionized water, and the material B comprises 0.35g of thioglycolic acid, 0.2g of vitamin C and 50g of deionized water. And (3) heating the three-neck flask to 15 ℃, adding 1.2g of hydrogen peroxide, stirring for 5min, then starting to dropwise add the materials A and B, respectively dripping for 30min and 40min, preserving the temperature for 20min, and adding dilution water after the reaction is finished to finally obtain the 40% solid water reducer with the double-arm side chain structure.
Example 3
Adding 88g of vinyl glycol ether, 1.4g of potassium bromide and 114g of potassium carbonate solid into a three-neck flask provided with a reflux condenser tube and a thermometer, stirring and heating to 45 ℃, adding 135g of bromopentanol dropwise under stirring until the potassium carbonate solid is completely dissolved, heating to 80 ℃, reacting for 2 hours, cooling to room temperature, neutralizing, washing with water and drying to obtain the hydroxyl-terminated alkyl ether.
159g of the obtained hydroxyl-terminated alkyl ether and 26g of lithium hydroxide solid are added into a three-neck flask provided with a reflux condenser tube and a thermometer, stirred and heated to 70 ℃, 57g of glycidol is added dropwise under stirring for reaction for 3 hours, and the unsaturated glycol ether is obtained after cooling to room temperature and filtering.
233g of the unsaturated glycol ether obtained above and 120g of solid potassium hydroxide were charged into a flask equipped with a reflux condenser and a thermometer, and heated to 100 ℃ with stirring, 4200g of ethylene oxide and 2610g of propylene oxide were introduced with stirring, reacted for 6 hours, and cooled to obtain a double-arm side chain structure monomer.
140g of the above-mentioned double-arm side chain structural monomer, 4.14g of sodium styrenesulfonate, and 90g of deionized water were placed in a three-necked flask equipped with a thermometer. Preparing materials A and B simultaneously, wherein the material A comprises 5.1g of acrylic acid and 30g of deionized water, and the material B comprises 0.32g of mercaptoethanol, 0.2g of vitamin C and 50g of deionized water. Heating a three-neck flask to 30 ℃, adding 1.2g of hydrogen peroxide and 0.01g of ferrous sulfate, stirring for 5min, then dropwise adding the materials A and B, respectively dropwise adding the materials A and B for 50min and 60min, preserving heat for 30min, and adding dilution water after the reaction is finished to finally obtain the 40% solid water reducer with the double-arm side chain structure.
Example 4
Adding 88g of vinyl glycol ether, 1.2g of sodium chloride and 78g of sodium ethoxide into a three-neck flask provided with a reflux condenser tube and a thermometer, stirring and heating to 45 ℃, when the vinyl glycol ether, the sodium chloride and the sodium ethoxide are completely dissolved, dropwise adding 62g of chlorohydrin under stirring, heating to 70 ℃, reacting for 2.5 hours, cooling to room temperature, neutralizing, washing with water and drying to obtain the hydroxyl-terminated alkyl ether.
115g of the hydroxyl-terminated alkyl ether obtained in the previous step and 43g of solid sodium hydroxide are added into a three-neck flask provided with a reflux condenser tube and a thermometer, the mixture is stirred and heated to 60 ℃, 58g of glycidol is added dropwise under stirring for reaction for 3 hours, and the unsaturated glycol ether is obtained after cooling to room temperature and filtration.
189g of the unsaturated glycol ether and 50g of solid sodium hydride are added into a flask provided with a reflux condenser tube and a thermometer, the temperature is raised to 90 ℃ by stirring, 4928g of ethylene oxide and 2784g of propylene oxide are introduced into the flask by stirring, the mixture reacts for 6 hours, and the monomer with the double-arm side chain structure is obtained by cooling.
160g of the above-mentioned monomer having a double-arm side chain structure and 120g of deionized water were placed in a three-necked flask equipped with a thermometer. A material A and a material B are prepared simultaneously, wherein the material A is 6.48g of acrylic acid and 40g of deionized water, and the material B is 1g of sodium methallylsulfonate and 50g of deionized water. And (3) heating the three-neck flask to 30 ℃, adding 0.7g of ammonium persulfate, stirring for 5min, then starting to dropwise add the materials A and B, respectively dropwise adding for 60min and 80min, preserving the temperature for 60min, and adding dilution water after the reaction is finished to finally obtain the 40% solid water reducer with the double-arm side chain structure.
The performance test of the invention:
and (3) clear pulp testing: according to GB8077-2000 'homogeneity test method for concrete admixture', the samples of examples 1-4 are used for net slurry fluidity test, and comparative samples 1-5 are used for net slurry fluidity test by using a conventional water reducing agent P6 of Changchenyu building materials Co., ltd in Shijiazhuang with different mixing amounts, wherein the water-cement ratio is 0.16, the cement using amount is 300g, and the cement is Emkensheng P.O42.5, and the dispersion performance under different mixing amounts is inspected. Also in comparison to the neat paste flow of the control at the conventional water-to-gel ratio (0.29), the neat paste test data is shown in table 1:
TABLE 1 neat paste test results
Figure 118165DEST_PATH_IMAGE010
And (4) conclusion: the data in table 1 show that the comparative sample has good dispersion performance in conventional slurry purification detection (0.29 water-cement ratio), but the dispersion performance is sharply reduced under the condition of reducing the water-cement ratio, the good dispersion effect cannot be achieved by increasing the folded-solid content, even under the condition of 0.3% folded-solid content, the dispersion performance does not have the trend of being obviously improved, the limit is reached, and the application requirement of the ultra-high strength concrete cannot be met by the conventional mother liquor. The initial neat paste fluidity of the cement paste in the examples 1,2, 3 and 4 of the invention reaches over 240mm under 0.1% of the folded solid content, has good dispersion performance, and can completely meet the dispersion of cement particles under low water-gel ratio.
And (3) testing concrete:
the cement is P.O.52.5 cheng; the coal ash is first-grade coal ash; s95 level mineral powder; the silica fume is used as a blending material, the sand is river sand, and the stones are 5-20mm continuous graded broken stones; the water reducing agents of the examples 1 to 4 are subjected to fresh concrete performance tests according to GB/T50080-2016 standard of Performance test methods for common concrete mixtures, comparative examples 1 to 4 adopt water reducing agents P6 with different folded and solid mixing amounts to compare the dispersion performance of the products, the viscosity of the concrete is reflected by the back-lifting time, and C120 is used for carrying out mix proportion experiments, wherein the mix proportion is shown in the following table 2, and the concrete performance data are respectively shown in the following table 3:
table 2: concrete mixing proportion
Figure 187752DEST_PATH_IMAGE011
Table 3: concrete performance test data
Figure 588778DEST_PATH_IMAGE012
And (4) conclusion: the data in Table 3 show that the comparative sample as a conventional water reducing agent has poor dispersion performance in the ultra-high-strength concrete, the construction requirements cannot be met when the doping amount is increased, the expansion degree is not increased after the doping amount reaches the limit, and the viscosity is larger. The concrete can achieve good dispersing performance under very low mixing amount in the embodiments 1,2, 3 and 4, and the concrete has small viscosity within a few seconds after being poured, thereby completely meeting the construction requirements of ultra-high strength concrete.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims (10)

1. A double-arm side chain structure monomer is characterized in that the molecular formula of the double-arm side chain structure monomer is as follows:
Figure QLYQS_1
；
in the above formula, n is more than or equal to 1 and less than or equal to 5, a is more than 90, b is more than 90 1 =
Figure QLYQS_2
Or
Figure QLYQS_3
，R 2 =
Figure QLYQS_4
Or
Figure QLYQS_5
。
2. The dual-arm side-chain structural monomer of claim 1, wherein: the molecular weight of the double-arm side chain structure monomer is 5000-8000.
3. The dual-arm side-chain structural monomer of claim 1 or 2, wherein: the proportion of the mole amount of the ethoxy groups of the double-arm side chain structural monomer to the total mole amount of the ethoxy groups and the propoxy groups is more than 70%.
4. A method for preparing a dual-arm side-chain structural monomer according to any one of claims 1 to 3, comprising the steps of:
mixing vinyl glycol ether, a catalyst and an alkaline compound, stirring for dissolving, then dropwise adding halogenated alkyl alcohol, heating, keeping the temperature, cooling to room temperature, washing with water and drying to obtain hydroxyl-terminated alkyl ether;
mixing the hydroxyl-terminated alkyl ether and an alkaline compound, stirring and heating, dripping glycidol, preserving heat, cooling to room temperature, and filtering to obtain unsaturated glycol ether;
and mixing the unsaturated glycol ether and an alkaline compound, stirring and heating, introducing ethylene oxide and/or propylene oxide, and cooling after the reaction is finished to obtain the double-arm side chain structure monomer.
5. The method for preparing a monomer with double-arm side chain structure according to claim 4, wherein: the catalyst comprises an alkali metal halide;
and/or the alkaline compound comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide and sodium ethoxide;
and/or, the halogenated alkyl alcohol comprises at least one of chlorohydrin, chloropropanol, chlorobutanol, chloropentanol, chlorohexanol, bromoethanol, bromopropanol, bromobutanol, bromopentanol and bromohexanol.
6. The method for preparing a monomer with double-arm side chain structure according to claim 4, wherein: the molar ratio of the vinyl glycol ether to the halogenated alkyl alcohol is 1.05-1.1.
7. The method for preparing a double-arm side-chain structural monomer according to any one of claims 4 to 6, wherein: the molar ratio of the hydroxyl-terminated alkyl ether to the glycidol is 1.2 to 1.3.
8. A water reducing agent is characterized in that: the raw materials for preparing the water reducing agent comprise the monomer with double-arm side chain structure and the unsaturated acid, wherein the molar ratio of the monomer with double-arm side chain structure to the unsaturated acid is 1.5-5.
9. The preparation method of the water reducer according to claim 8, characterized by comprising the following steps:
mixing the aqueous solution of the monomer with the double-arm side chain structure with the aqueous solution of an oxidant, then dropwise adding the solution A and the solution B, and obtaining the water reducer after the reaction is finished;
the solution A is an aqueous solution of unsaturated acid, and the solution B is an aqueous solution of reducing agent and chain transfer agent.
10. The method for preparing the water reducing agent according to claim 9, characterized in that: the unsaturated acid comprises at least one of acrylic acid, methacrylic acid, fumaric acid, maleic anhydride and 2-acrylamide-2-methylpropanesulfonic acid;
and/or the reducing agent comprises at least one of vitamin C, ferrous sulfate and sodium hypophosphite;
and/or the oxidant comprises at least one of hydrogen peroxide, ammonium persulfate and potassium persulfate;
and/or, the chain transfer agent comprises at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, and sodium methallylsulfonate.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115516A (en) * 2010-12-22 2011-07-06 江苏博特新材料有限公司 Preparation method for comb-shaped copolymer cement dispersant, monomer used therein and prepared comb-shaped copolymer cement dispersant
CN113683738A (en) * 2021-08-25 2021-11-23 佳化化学科技发展（上海）有限公司 Polycarboxylate superplasticizer and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102115516A (en) * 2010-12-22 2011-07-06 江苏博特新材料有限公司 Preparation method for comb-shaped copolymer cement dispersant, monomer used therein and prepared comb-shaped copolymer cement dispersant
CN113683738A (en) * 2021-08-25 2021-11-23 佳化化学科技发展（上海）有限公司 Polycarboxylate superplasticizer and preparation method thereof

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