CN112552517A - Hyperbranched polymer viscosity reducer for high-strength concrete and preparation method thereof - Google Patents

Hyperbranched polymer viscosity reducer for high-strength concrete and preparation method thereof Download PDF

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CN112552517A
CN112552517A CN202011320411.0A CN202011320411A CN112552517A CN 112552517 A CN112552517 A CN 112552517A CN 202011320411 A CN202011320411 A CN 202011320411A CN 112552517 A CN112552517 A CN 112552517A
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compound
hyperbranched polymer
viscosity reducer
polymer viscosity
strength concrete
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CN112552517B (en
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高育欣
杨文�
王福涛
曾超
王军
刘明
毕耀
张磊
王鹏
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Building Materials Science Research Institute Co Ltd of China West Construction Group Co Ltd
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Building Materials Science Research Institute Co Ltd of China West Construction Group 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • 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
    • 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
    • C04B2103/34—Flow improvers

Abstract

The invention relates to a hyperbranched polymer viscosity reducer for high-strength concrete and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out ring-opening reaction on a benzene ring compound with two or more primary amino functional groups and epoxy chloropropane to obtain a compound A; step 2: the compound A and solid alkali carry out ring closure reaction to obtain a glycidylamine compound B1(ii) a And step 3: reacting glycidyl amine compound B1Performing ring opening and ring closing reaction for M times to obtain compound B1+MM is not less than 0; and 4, step 4: reacting glycidyl amine compound B1+MThe needed hyperbranched polymer viscosity reducer can be obtained by the reaction of monomethyl ether and a sodium hydroxide solution with the mass concentration of 50 wt%; the invention effectively reduces the winding among the chains of the polycarboxylic acid water reducing agent, improves the occupation rate of unadsorbed sites on the surface of cement particles, improves the dispersion performance of the water reducing agent and the surface of gelled material particles by virtue of the characteristics of low viscosity, high dissolution and larger space volume of the hyperbranched polymerThickness of the adsorption layer of the face.

Description

Hyperbranched polymer viscosity reducer for high-strength concrete and preparation method thereof
Technical Field
The invention relates to the field of concrete admixtures, in particular to a hyperbranched polymer viscosity reducer for high-strength concrete and a preparation method thereof.
Background
With the development of the building industry in China, high-rise and super high-rise buildings are increasing day by day. The super high-rise pumping concrete has the characteristics of high specific strength, large load capacity, excellent durability, resource and energy conservation and the like. However, in actual production, the water-cement ratio is low, the using amount of the cementing material is large, and the types of mineral admixtures are various, so that the viscosity of a concrete mixture is large, and a series of construction problems such as concrete stirring, transportation, pumping and the like are caused.
Low viscosity and high fluidization are typical characteristics of modern concrete and are key guarantees for the technical development of high-rise and super high-rise buildings. The most common methods for lowering the viscosity of concrete at the present stage include: the mixing amount of the water reducing agent is increased, the grading of rubber particles is optimized, and the air entraining agent, the viscosity reducer and the like are compounded. The improvement of the mixing amount can effectively improve the fluidity of the concrete and reduce the molding viscosity, but can easily cause the new problems of segregation, bottom scraping, excessive slow setting and the like of the concrete. The cement mortar has optimized rubber material grain composition and can reduce the viscosity of concrete, but the prior raw materials are short of high-quality mineral admixture and have certain limitation on ultra-high performance concrete. The air entraining agent is mixed in, so that the friction force among aggregates is reduced by virtue of bubbles, so that the viscosity of concrete is reduced, but the universality of air entraining and viscosity reduction is low due to the complexity and diversity of concrete raw materials, and the adverse effect is easily generated on the strength of the concrete. The organic viscosity reducer which is newly appeared in recent years can obviously reduce the yield stress of cement paste, but can not effectively reduce the viscosity of the cement paste and improve the flow rate of the paste.
At present, the viscosity reduction type polycarboxylate superplasticizer receives general attention, and a special functional group is introduced, the length of a side chain is controlled, and the thickness of an adsorption layer of the polycarboxylate superplasticizer on the surface of cement particles is adjusted to release free water so as to reduce the viscosity of concrete. Aiming at the low water-cement ratio of the ultra-high-strength concrete, two technical means of viscosity reduction type polycarboxylate superplasticizers and inorganic admixtures are often adopted for compounding, but the polycarboxylate superplasticizer with a comb-shaped structure has high intrinsic viscosity and more residual slurry amount, so that the slurry viscosity is high. The hyperbranched polymer has good molecular plasticity and low intrinsic viscosity, and can effectively reduce the chain entanglement effect among polymers and reduce the viscosity of the polymers. The hyperbranched polymer can effectively reduce the chain winding effect among polymers, improve the spatial repulsion of the water reducing agent, improve the dispersion performance and reduce the mixing amount of the water reducing agent. The hyperbranched polymer has a molecular structure similar to a sphere, has a thicker adsorption layer on the surfaces of the gelled material particles, can effectively compress the thickness of a solvation layer to release free water, and reduces the viscosity of concrete. Therefore, the development of hyperbranched polymer viscosity reducers is imminent.
In recent years, hyperbranched polymers have a highly branched three-dimensional spherical structure and many reactive end groups exhibit properties distinct from other molecules and have received much attention from researchers. For example, the carboxyl-terminated hyperbranched retarders prepared by CN201811088667.6 and CN201811089263.9 have controllable retardation time and hyperbranched algebra, and can effectively improve the fluidity of concrete. However, polyhydroxy groups in the molecular structure are easy to form intermolecular and intramolecular hydrogen bonds, and bound free water is easy to increase the viscosity of concrete. The non-adsorption linear micromolecules reported by Johann Plank improve the interfacial force of cement particles, accelerate the wetting property of the water reducing agent and the surfaces of the cement particles, improve the fluidity of concrete, reduce the viscosity of a system, but the gas content of the concrete is increased due to excessive use amount. Hamada developed a novel polymer (NHBP type) of multi-branched structure by introducing two anionically acting compounds. The adsorption capacity of the polymer on particles with different surface characteristics in the gelled material is increased, the three-dimensional network structure of cement particles is broken, the rheological property is improved, and the viscosity is reduced. For example, CN201911179520.2 discloses a micro-crosslinked polycarboxylic acid prepared from unsaturated acid, unsaturated acid anhydride, crosslinking agent, and polyether compound, which increases the thickness of the adsorption layer on the surface of the gel material particles to release free water to reduce the concrete viscosity. Although the existing hyperbranched polymer is used as a retarder, the existing hyperbranched polymer is not used as a hyperbranched viscosity reducer.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hyperbranched polymer viscosity reducer for high-strength concrete, which is used for high-strength concrete and can reduce the mixing amount of a water reducer and the viscosity of the concrete, and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a hyperbranched polymer viscosity reducer for high-strength concrete comprises the following steps:
step 1: dissolving a benzene ring compound with two or more primary amino functional groups in an aprotic polar solvent, adding a catalyst, and heating to 60-100 ℃; then dripping an epoxy chloropropane solution, fully reacting, removing the solvent and drying to obtain a compound A; wherein the molar ratio of the benzene ring compound to the epoxy chloropropane is 1: 3-10;
step 2: dissolving the compound A in the step 1 in an aprotic polar solvent, adding solid alkali for multiple times, fully reacting, filtering to remove generated salt, removing the solvent, and drying to obtain a glycidylamine compound B1(ii) a The molar ratio of the solid alkali to the epichlorohydrin in the step 1 is 1: 1;
and step 3: subjecting the glycidylamine compound B formed in step 2 to1Dissolving in an aprotic polar solvent; repeating the step 1 and the step 2M times to obtain a glycidylamine compound B1+M(ii) a Wherein M is more than or equal to 0; wherein the glycidyl amine compound B1+iThe molar ratio of the benzene ring compound is as follows: 1: 3-100; i is more than or equal to 0;
and 4, step 4: the glycidyl amine compound B obtained in the step 31+MUniformly mixing monomethyl ether and 50 wt% sodium hydroxide solution, and fully reacting at 60-130 ℃ to obtain the required hyperbranched polymer viscosity reducer; the glycidyl amine compound B1+MThe mol ratio of the methyl ether to the methyl ether is 1: 3-200; the addition amount of the sodium hydroxide solution is 0.1-5.0 wt% of the mass of the monomethyl ether.
Further, the benzene ring compound is one of 1,3, 5-triaminobenzene, p-phenylenediamine, p-diaminobiphenyl, 4 '-diaminodiphenylmethane, 1, 4-xylylenediamine, 2,4, 6-triethylbenzene-1, 3, 5-trimethylamine, and 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine.
Further, the aprotic polar solvent is one or a mixture of two or more of benzene, toluene, xylene, cyclohexane, chloroform, dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-3.4, 5, 6-tetrahydro-2-pyrimidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, N-methylpyrrolidone and acetonitrile in any proportion.
Further, the catalyst is one or a mixture of two or more of triethylbenzylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, tetrabutylammonium p-toluenesulfonate, dodecyldimethylbenzylammonium chloride, tetrapropylammonium bromide, benzyltrimethylammonium bromide and tributylmethylammonium bromide in any proportion.
Furthermore, the addition amount of the catalyst is 0.01-0.1 wt% of the total mass of the reaction raw materials in the reaction process.
Further, the solid alkali is one or a mixture of two or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride and potassium hydride in any proportion.
Further, the monomethyl ether is one or a mixture of two of polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether in any proportion.
Further, slowly dripping the epoxy chloropropane solution in the step 1, wherein the dripping time is 0.1-1.0 h.
The hyperbranched polymer viscosity reducer for high-strength concrete is characterized in that the hyperbranched polymer viscosity reducer accounts for 0.01-2 wt% of the total solid content of an additive.
The invention has the beneficial effects that:
(1) the hyperbranched polymer viscosity reducer for high-strength concrete prepared by the invention has the characteristics of special branched topological molecular structure, low intrinsic viscosity, large space volume and the like; the intermolecular chain winding effect of the polycarboxylate superplasticizer is effectively weakened, the spatial repulsion of the polycarboxylate superplasticizer is increased, the dispersing performance of the polycarboxylate superplasticizer is improved, the using amount of the polycarboxylate superplasticizer is reduced, and the influence of the residual polycarboxylate superplasticizer on the viscosity of slurry is weakened;
(2) the hyperbranched polymer viscosity reducer for high-strength concrete, prepared by the invention, occupies adsorption sites on the surfaces of the gelled material particles which are not occupied by the polycarboxylate water reducer, increases the thickness of the adsorption layer on the surfaces of the gelled material particles, weakens the solvation thickness of the particle surfaces, releases free water and reduces the viscosity of concrete;
(3) the hyperbranched polymer viscosity reducer for high-strength concrete, which is prepared by the invention, can effectively regulate and control the arm number and the arm length of the hyperbranched polymer by regulating the size of M according to actual requirements; the repulsion force on the surfaces of the gelled material particles is effectively improved, and the fluidity of the concrete is improved;
(4) hydroxyl groups are introduced into the hyperbranched polymer viscosity reducer for high-strength concrete, so that cement hydration can be effectively delayed, the plasticity retention of the concrete is improved, the hydration temperature of the high-strength concrete is controlled to be increased, and the cracking risk of the high-strength concrete is reduced;
(5) in the preparation method, the raw material cost is low, the synthesis process is simple, the environment is friendly, and the preparation method is suitable for popularization and application.
Drawings
FIG. 1 is a graph of the viscosity of a cement pore fluid after compounding a hyperbranched polymer viscosity reducer prepared in an embodiment of the present invention with a polycarboxylic acid water reducer.
Fig. 2 is a thickness diagram of an adsorption layer on nano calcium silicate hydrate after the hyperbranched polymer viscosity reducer prepared in the embodiment of the present invention is compounded with a polycarboxylic acid water reducer.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
A preparation method of a hyperbranched polymer viscosity reducer for high-strength concrete comprises the following steps:
step 1: ring-opening reaction of primary amine group and epoxy chloropropane: dissolving a benzene ring compound with two or more primary amino functional groups in an aprotic polar solvent, adding a catalyst, and heating to 60-100 ℃; then dripping an epoxy chloropropane solution, fully reacting, removing the solvent and drying to obtain a compound A; wherein the molar ratio of the benzene ring compound to the epoxy chloropropane is 1: 3-10.
The benzene ring compound is one of 1,3, 5-triaminobenzene, p-phenylenediamine, p-diaminobiphenyl, 4 '-diaminodiphenylmethane, 1, 4-xylylenediamine, 2,4, 6-triethylbenzene-1, 3, 5-trimethylamine, and 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine. The aprotic polar solvent is one or a mixture of two or more of benzene, toluene, xylene, cyclohexane, chloroform, dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-3.4, 5, 6-tetrahydro-2-pyrimidone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, N-methylpyrrolidone and acetonitrile in any proportion.
The solvent of the epichlorohydrin is a polar cosolvent, and the polar cosolvent is one or a mixture of two or more of ethanol, isopropanol, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, diethyl ether, chloroform and trichloroethylene in any proportion. Step 1, the reaction time is not limited, and the reaction can be completed; the reaction time is preferably 1.0-5.0 h.
Step 2: preparation of glycidyl amine compound by ring closure reaction: dissolving the compound A in the step 1 in an aprotic polar solvent, adding solid alkali for multiple times, fully reacting, filtering to remove generated salt, removing the solvent, and drying to obtain a glycidylamine compound B1(ii) a The molar ratio of the solid base to the epichlorohydrin in the step 1 is 1: 1.
The solid alkali is one or a mixture of two or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride and potassium hydride in any proportion. N is preferably three times, but may be divided into a plurality of times; the solid base was added in three equal portions. The reaction time in the step 2 is not limited, and is preferably 1 hour on the basis of complete reaction, and the reaction is filtered after standing; the number of times of addition of the solid base herein can be adjusted according to actual needs, and the number of times of addition is 3 in the following examples of the present invention.
And step 3: subjecting the glycidylamine compound B formed in step 2 to1Dissolving in an aprotic polar solvent; repeating the step 1 and the step 2M times to obtain a glycidylamine compound B1+M(ii) a Wherein M is more than or equal to 0; wherein the glycidyl amine compound B1+iThe molar ratio of the benzene ring compound is as follows: 1: 3-100; i is more than or equal to 0;
glycidylamine Compound B produced in step 21Performing ring-opening reaction with epichlorohydrin, and preparing glycidylamine compound B by ring-closing reaction2(ii) a And so on. The reaction time is not limited, and is preferably 1.0-4.0 h in the ring-opening reaction under the condition of complete reaction; the reaction time in the ring-closure reaction is preferably 1 hour. M can be any value theoretically, and is optimally 0, 1, 2, 3,4,5 through experiments.
The catalyst is one or a mixture of two or more of triethyl benzyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium hydroxide, hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, tetrabutyl p-toluene ammonium sulfonate, dodecyl dimethyl benzyl ammonium chloride, tetrapropyl ammonium bromide, benzyl trimethyl ammonium bromide and tributyl methyl ammonium bromide in any proportion. The addition amount of the catalyst is 0.01-0.1 wt% of the total mass of the reaction raw materials in the reaction process.
And 4, step 4: the glycidyl amine compound B obtained in the step 31+MUniformly mixing monomethyl ether and 50 wt% sodium hydroxide solution, and fully reacting at 60-130 ℃ to obtain the required hyperbranched polymer viscosity reducer; the glycidyl amine compound B1+MThe mol ratio of the methyl ether to the methyl ether is 1: 3-200; the addition amount of the sodium hydroxide solution is 0.1-5.0 wt% of the mass of the monomethyl ether.
The monomethyl ether is one or a mixture of two of polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether in any proportion. The number average molecular weight of the monomethyl ether is one or more of 600g/mol, 750g/mol, 1000g/mol and 2000 g/mol.
Example 1
The hyperbranched polymer viscosity reducer for the high-strength concrete is prepared according to the following steps:
step 1: weighing 0.5mol of 1,3, 5-triaminobenzene and dissolving in an aprotic polar solvent; then adding mixed catalyst formed from triethyl benzyl ammonium chloride and tetraethyl ammonium bromide. After heating to 80 ℃, 3.0mol of epichlorohydrin is dripped in 0.5 hour, and then the temperature is kept for 2.0 hours. The resulting solution was subjected to vacuum drying at room temperature for 24.0 hours after removing the solvent by a rotary evaporator to obtain compound a.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2-pyrimidone and ethylene glycol dimethyl ether.
Step 2: weighing 0.5mol of compound A, dissolving the compound A in an aprotic polar solvent, and adding 3.0mol of sodium hydroxide in three batches of equimolar amount; after the reaction for 1.0 hour, the reaction mixture was allowed to stand, the formed salt was filtered off, and the solvent was removed from the resulting solution by a rotary evaporator, followed by vacuum drying at room temperature for 24.0 hours to obtain Compound B. And (3) testing the epoxy value of the compound B by a chemical dropping point method at the reaction end point, and judging as the reaction end point after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of dimethyl sulfoxide, ethylene glycol dimethyl ether, cyclohexane and chloroform.
And step 3: weighing 0.1mol of the compound B and 0.6mol of polyethylene glycol monomethyl ether (MPEG-2000, molecular weight 2000g/mol), adding 12.0g of sodium hydroxide solution with mass concentration of 50 wt%, heating to 80 ℃, and keeping the temperature for 2 hours to obtain the hyperbranched polymer viscosity reducer.
Example 2
The hyperbranched polymer viscosity reducer for the high-strength concrete is prepared according to the following steps:
step 1: weighing 0.5mol of p-phenylenediamine to be dissolved in an aprotic polar solvent; then adding mixed catalyst formed from triethyl benzyl ammonium chloride and tetraethyl ammonium bromide. After heating to 80 ℃, 2.0mol of epichlorohydrin is dripped in 0.5 hour, and then the temperature is kept for 2.0 hours. The resulting solution was subjected to vacuum drying at room temperature for 24.0 hours after removing the solvent by a rotary evaporator to obtain compound a.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of dimethyl sulfoxide, chloroform and 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2-pyrimidone.
Step 2: weighing 0.5mol of compound A, dissolving the compound A in an aprotic polar solvent, and adding 2.0mol of sodium hydroxide in three batches of equimolar amount; after the reaction for 1.0 hour, the reaction mixture was allowed to stand, the formed salt was filtered off, and the solvent was removed from the resulting solution by a rotary evaporator, followed by vacuum drying at room temperature for 24.0 hours to obtain Compound B. And (3) testing the epoxy value of the compound B by a chemical dropping point method at the reaction end point, and judging as the reaction end point after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of benzene, ethylene glycol dimethyl ether, cyclohexane and chloroform.
And step 3: weighing 0.1mol of the compound B and 0.4mol of polyethylene glycol monomethyl ether (MPEG-600, molecular weight 600g/mol), adding 4.8g of sodium hydroxide solution with mass concentration of 50 wt%, heating to 70 ℃, and keeping the temperature for 2 hours to obtain the hyperbranched polymer viscosity reducer.
Example 3
The hyperbranched polymer viscosity reducer for the high-strength concrete is prepared according to the following steps:
step 1: weighing 0.5mol of 2,4, 6-triethylbenzene-1, 3, 5-trimethylamine, and dissolving in an aprotic polar solvent; then adding mixed catalyst formed from triethyl benzyl ammonium chloride and tetraethyl ammonium bromide. After heating to 90 ℃, 3.0mol of epichlorohydrin is dripped in 0.5 hour, and then the temperature is kept for 2.0 hours. The resulting solution was subjected to vacuum drying at room temperature for 24.0 hours after removing the solvent by a rotary evaporator to obtain compound a.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of cyclohexane, N-dimethylformamide and 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2-pyrimidone.
Step 2: weighing 0.5mol of compound A, dissolving the compound A in an aprotic polar solvent, and adding 3.0mol of sodium hydroxide in three batches of equimolar amount; after the reaction for 1.0 hour, the reaction mixture was allowed to stand, the formed salt was filtered off, and the solvent was removed from the resulting solution by a rotary evaporator, followed by vacuum drying at room temperature for 24.0 hours to obtain Compound B. And (3) testing the epoxy value of the compound B by a chemical dropping point method at the reaction end point, and judging as the reaction end point after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of ethylene glycol dimethyl ether, cyclohexane and chloroform.
And step 3: weighing 0.1mol of the compound B and 0.6mol of polyethylene glycol monomethyl ether (MPEG-600, molecular weight 600g/mol), adding 10.8g of sodium hydroxide solution with mass concentration of 50 wt%, heating to 70 ℃, and keeping the temperature for 2.5 hours to obtain the hyperbranched polymer viscosity reducer.
Example 4
The hyperbranched polymer viscosity reducer for the high-strength concrete is prepared according to the following steps:
step 1: weighing 0.5mol of 1,3, 5-triaminobenzene and dissolving in an aprotic polar solvent; then adding a mixed catalyst consisting of tetraethylammonium hydroxide and tetraethylammonium bromide. After heating to 70 ℃, 3.0mol of epichlorohydrin is dripped in 0.5 hour, and then the temperature is kept for 2.0 hours. The resulting solution was subjected to vacuum drying at room temperature for 24.0 hours after removing the solvent by a rotary evaporator to obtain compound a.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of dimethyl sulfoxide, N-dimethylformamide and 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2-pyrimidone.
Step 2: weighing 0.5mol of compound A, dissolving the compound A in an aprotic polar solvent, and adding 3.0mol of potassium hydroxide in three batches of equimolar amount; reacting for 1.0 hr, standing, filtering to remove the salt, removing solvent from the solution by rotary evaporator, and vacuum drying at room temperature for 24.0 hr to obtain compound B1. Chemical dropping method is used for the compound B at the end point of the reaction1The epoxy value of (A) is tested, and the reaction end point is judged after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of benzene, ethylene glycol dimethyl ether, cyclohexane and chloroform.
And step 3: 0.5mol of compound B is weighed1And 6.0mol of 1,3, 5-triaminobenzene are dissolved in an aprotic polar solvent. Then adding a mixed catalyst of tetraethyl ammonium hydroxide and tetraethyl ammonium bromide. Heating to 90 ℃, preserving heat for 2.0h, after the heat preservation is finished, dripping 6.0mol of epichlorohydrin within 0.5 h, and preserving heat for 2.0 h. The resulting solution was subjected to solvent removal by a rotary evaporator and vacuum dried at room temperature for 24.0 hours to give compound C.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of dimethyl sulfoxide, ethylene glycol dimethyl ether and cyclohexane.
And 4, step 4: weighing 0.5mol of compound C, dissolving in aprotic polar solvent, adding 6.0mol of sodium hydroxide in three equal molar amounts, reacting for 1.0h, standing, filtering to remove the generated salt, removing the solvent from the obtained solution by a rotary evaporator, and vacuum drying at room temperature for 24.0 h to obtain compound B2The reaction end point is used for the compound B by a chemical dropping point method2The epoxy value of (A) is tested, and the reaction end point is judged after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of ethylene glycol dimethyl ether, cyclohexane and chloroform.
And 5: 0.1mol of compound B is weighed2And 2.4mol of polyethylene glycol monomethyl ether (MPEG-600, molecular weight 600g/mol), adding 40.6g of sodium hydroxide solution with mass concentration of 50 wt%, heating to 60 ℃, and keeping the temperature for 2 hours to obtain the hyperbranched polymer viscosity reducer.
Example 5
The hyperbranched polymer viscosity reducer for the high-strength concrete is prepared according to the following steps:
step 1: weighing 0.5mol of 2,4, 6-triethylbenzene-1, 3, 5-trimethylamine, and dissolving in an aprotic polar solvent; then adding mixed catalyst formed from triethyl benzyl ammonium chloride and tetraethyl ammonium bromide. After heating to 90 ℃, 3.0mol of epichlorohydrin is dripped in 0.5 hour, and then the temperature is kept for 2.0 hours. The resulting solution was subjected to vacuum drying at room temperature for 24.0 hours after removing the solvent by a rotary evaporator to obtain compound a.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of cyclohexane, N-dimethylformamide and 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2-pyrimidone.
Step 2: 0.5mol of Compound A is weighed out and dissolved inAdding 3.0mol of sodium hydroxide into the aprotic polar solvent in three batches in equal molar quantity; reacting for 1.0 hr, standing, filtering to remove the salt, removing solvent from the solution by rotary evaporator, and vacuum drying at room temperature for 24.0 hr to obtain compound B1. Chemical dropping method is used for the compound B at the end point of the reaction1The epoxy value of (A) is tested, and the reaction end point is judged after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of ethylene glycol dimethyl ether, cyclohexane and chloroform.
And step 3: 0.5mol of compound B is weighed1And 6.0mol of 2,4, 6-triethylbenzene-1, 3, 5-trimethylamine are dissolved in an aprotic polar solvent. Then adding a mixed catalyst of tetraethyl ammonium hydroxide and tetraethyl ammonium bromide. After heating to 90 ℃, 6.0mol of epichlorohydrin is dripped in 0.5 hour, and then the temperature is kept for 2.0 hours. The resulting solution was subjected to solvent removal by a rotary evaporator and vacuum dried at room temperature for 24.0 hours to give compound C.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of dimethyl sulfoxide, ethylene glycol dimethyl ether and cyclohexane.
And 4, step 4: weighing 0.5mol of compound C, dissolving in aprotic polar solvent, adding 6.0mol of sodium hydroxide in three equal molar amounts, reacting for 1.0h, standing, filtering to remove the generated salt, removing the solvent from the obtained solution by a rotary evaporator, and vacuum drying at room temperature for 24.0 h to obtain compound B2The reaction end point is used for the compound B by a chemical dropping point method2The epoxy value of (A) is tested, and the reaction end point is judged after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of ethylene glycol dimethyl ether, cyclohexane and chloroform.
And 5: 0.1mol of compound B is weighed2And 2.4mol of 2,4, 6-triethylbenzene-1, 3, 5-trimethylamine are dissolved in an aprotic polar solvent; then adding a mixed catalyst of tetraethylammonium hydroxide and tetraethylammonium bromide, heating to 100 ℃, preserving heat for 2.0 hours, after the heat preservation is finished, dropwise adding 6.0mol of epoxy chloropropane within 0.5 hour, and preserving heat for 2.0 hours. The resulting solution was subjected to solvent removal by a rotary evaporator and vacuum dried at room temperature for 24.0 hours to give compound C.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of dimethyl sulfoxide, ethylene glycol dimethyl ether and cyclohexane.
Step 6: weighing 0.1mol of compound D, dissolving in aprotic polar solvent, adding 9.6mol of sodium hydroxide in three equal molar amounts, reacting for 1.0h, standing, filtering to remove the generated salt, removing the solvent from the obtained solution by a rotary evaporator, and vacuum drying at room temperature for 24.0 h to obtain compound B3The reaction end point is used for the compound B by a chemical dropping point method3The epoxy value of (A) is tested, and the reaction end point is judged after the maximum epoxy value appears.
The amount of the aprotic polar solvent to be used is not particularly limited, and is generally such that the solid raw material can be dissolved. The amount of the solid raw material may be 50 to 1000 parts by weight, and in the present embodiment, 100 parts by weight is preferable. The aprotic polar solvent is a mixed solvent composed of ethylene glycol dimethyl ether, cyclohexane and chloroform.
And 7: 0.1mol of compound B is weighed3And 9.6mol of polyethylene glycol monomethyl ether (MPEG-1000, molecular weight 1000g/mol), adding 85.6g of sodium hydroxide solution with mass concentration of 50 wt%, heating to 90 ℃, and keeping the temperature for 2 hours to obtain the hyperbranched polymer viscosity reducer.
Performance test analysis: after the hyperbranched polymer viscosity reducer prepared in the embodiment 1-5 is compounded with a commercial water reducer, the concrete working performance and mechanical performance are tested. The performance of the concrete mixture is tested by referring to ' test method standard of common concrete mixture ' GB/T50080-2002, test method standard of common concrete mechanical property ' GB/T500821-2002, and ' technical specification for application of self-sealing concrete ' JGJ/T283-2012, CECS 203-.
The test results are shown in table 1, and the water reducing agent is compounded according to the high water reducing type mother liquor: comprehensive mother liquor: and (3) configuring the slump-retaining mother liquor in a ratio of 3:5: 2. The solid contents of the three mother liquids are respectively 50%, 40% and 50%, and the hyperbranched polymer viscosity reducer accounts for 0.5% of the total solid content of the compounded water reducer.
The concrete formula is as follows: 520kg of Lardue P.O 42.5 cement, 60kg of I-grade fly ash, 30 kg of silica fume, 750kg of machine sand (fineness modulus of 2.9), 1000kg of stones and 0.22 of water-cement ratio.
TABLE 1 concrete Performance comparison data
Figure BDA0002792712750000101
Comparative example 1 is a compounded water reducer without hyperbranched polymer viscosity reducer. Examples formulations using water reducing agents were the same in the proportion of hyperbranched viscosity reducing polymers.
As can be seen from Table 1, under the same conditions of the initial state of the concrete, the concrete of examples 1-5 is used in a lower amount than that of comparative example 1. The synthesized hyperbranched polymer viscosity reducer can effectively improve the dispersing capacity of the water reducer on the cementing material. In the embodiment, the concrete fluidity and slump retaining performance of the added hyperbranched polymer viscosity reducer are enhanced. Slump loss time and T500The time was less than that of comparative example 1. The hyperbranched polymer viscosity reducer prepared by the invention has obviously enhanced dispersion and better viscosity reduction effect after being compounded with a water reducing agent. Compared with the viscosity reducer without hyperbranched polymer, the viscosity reducer doped with the hyperbranched polymer has the advantages that the doping amount is reduced by more than 8 percent, the slump loss time is shortened by 57 to 71 percent, and T500The time is shortened by 2-5 s, and the viscosity reduction effect is obvious. Blending in Table 1The change rule of the collapse falling time of the concrete is consistent with the change rule of the concrete in figures 1 and 2. Experimental results show that the viscosity of the concrete can be effectively reduced by reducing the viscosity of the pore liquid and increasing the thickness of the adsorption layer on the surface of the particles.
FIG. 1 is a graph of the viscosity of a cement pore fluid after compounding a hyperbranched polymer viscosity reducer prepared in an embodiment of the present invention with a polycarboxylic acid water reducer. Fig. 2 is a thickness diagram of an adsorption layer on nano calcium silicate hydrate after the hyperbranched polymer viscosity reducer prepared in the embodiment of the present invention is compounded with a polycarboxylic acid water reducer. As can be seen from the figure, the viscosity of the polycarboxylate water reducer can be effectively reduced by more than 20% by adding the hyperbranched polymer viscosity reducer, and the thickness of the adsorption layer is increased by more than 30%.
The hyperbranched polymer viscosity reducer prepared by the invention has the characteristics of special branched topological molecular structure, low intrinsic viscosity, large space volume and the like, effectively weakens the intermolecular chain winding effect of the polycarboxylic acid water reducer, increases the space repulsion of the polycarboxylic acid water reducer, improves the dispersion performance of the polycarboxylic acid water reducer, reduces the using amount of the water reducer, and weakens the influence of the residual polycarboxylic acid water reducer on the viscosity of slurry. The hyperbranched polymer viscosity reducer occupies adsorption sites on the surfaces of the gelled material particles, which are not occupied by the polycarboxylate water reducer, increases the thickness of the adsorption layer on the surfaces of the gelled material particles, weakens the thickness of the solvation layer on the surfaces of the particles, releases free water, and reduces the viscosity of concrete. The hyperbranched polymer viscosity reducer prepared by the invention can effectively regulate and control the arm number and the arm length of the hyperbranched polymer according to actual requirements, effectively improve the electrostatic force and repulsive force of concrete particles, and improve the fluidity of concrete. The introduced polyhydroxy group can effectively delay cement hydration, improve concrete plasticity retention, control hydration temperature rise of high-strength concrete and reduce cracking risk of the high-strength concrete. In addition, the related raw materials have low cost, the synthesis process is simple and convenient, and the method is environment-friendly and suitable for popularization and application. The hyperbranched polymer is used as a viscosity reducer and is applied to high-strength concrete with strength grade of C60-C120, and the hyperbranched polymer viscosity reducer accounts for 0.01-2% of the total solid content of the admixture.

Claims (9)

1. A preparation method of a hyperbranched polymer viscosity reducer for high-strength concrete is characterized by comprising the following steps:
step 1: dissolving a benzene ring compound with two or more primary amino functional groups in an aprotic polar solvent, adding a catalyst, and heating to 60-100 ℃; then dripping an epoxy chloropropane solution, fully reacting, removing the solvent and drying to obtain a compound A; wherein the molar ratio of the benzene ring compound to the epoxy chloropropane is 1: 3-10;
step 2: dissolving the compound A in the step 1 in an aprotic polar solvent, adding solid alkali for multiple times, fully reacting, filtering to remove generated salt, removing the solvent, and drying to obtain a glycidylamine compound B1(ii) a The molar ratio of the solid alkali to the epichlorohydrin in the step 1 is 1: 1;
and step 3: subjecting the glycidylamine compound B formed in step 2 to1Dissolving in an aprotic polar solvent; repeating the step 1 and the step 2M times to obtain a glycidylamine compound B1+M(ii) a Wherein M is more than or equal to 0; wherein the glycidyl amine compound B1+iThe molar ratio of the benzene ring compound is as follows: 1: 3-100; i is more than or equal to 0;
and 4, step 4: the glycidyl amine compound B obtained in the step 31+MUniformly mixing monomethyl ether and 50 wt% sodium hydroxide solution, and fully reacting at 60-130 ℃ to obtain the required hyperbranched polymer viscosity reducer; the glycidyl amine compound B1+MThe mol ratio of the methyl ether to the methyl ether is 1: 3-200; the addition amount of the sodium hydroxide solution is 0.1-5.0 wt% of the mass of the monomethyl ether.
2. The method for preparing a hyperbranched polymer viscosity reducer for high-strength concrete according to claim 1, wherein the benzene ring compound is one of 1,3, 5-triaminobenzene, p-phenylenediamine, p-diaminobiphenyl, 4 '-diaminodiphenylmethane, 1, 4-xylylenediamine, 2,4, 6-triethylbenzene-1, 3, 5-trimethylamine, 4',4 "- (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine.
3. The method for preparing the hyperbranched polymer viscosity reducer for high-strength concrete according to claim 1, wherein the aprotic polar solvent is one or a mixture of two or more of benzene, toluene, xylene, cyclohexane, chloroform, dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-3.4, 5, 6-tetrahydro-2-pyrimidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, N-methylpyrrolidone and acetonitrile in any proportion.
4. The method for preparing the hyperbranched polymer viscosity reducer for high-strength concrete according to claim 1, wherein the catalyst is one or a mixture of two or more of triethylbenzylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, tetrabutylammonium p-toluenesulfonate, dodecyldimethylbenzylammonium chloride, tetrapropylammonium bromide, benzyltrimethylammonium bromide and tributylmethylammonium bromide in any proportion.
5. The preparation method of the hyperbranched polymer viscosity reducer for high-strength concrete according to claim 1, wherein the addition amount of the catalyst is 0.01-0.1 wt% of the total mass of the reaction raw materials in the reaction process.
6. The method for preparing the hyperbranched polymer viscosity reducer for high-strength concrete according to claim 1, wherein the solid alkali is one or a mixture of two or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride and potassium hydride in any proportion.
7. The method for preparing the hyperbranched polymer viscosity reducer for high-strength concrete according to claim 1, wherein the monomethyl ether is one or a mixture of two of polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether in any proportion.
8. The preparation method of the hyperbranched polymer viscosity reducer for high-strength concrete according to claim 1, wherein the epoxy chloropropane solution is slowly dripped during the step 1, and the dripping time is 0.1-1.0 h.
9. The hyperbranched polymer viscosity reducer for high-strength concrete, which is obtained by the preparation method according to any one of claims 1 to 8, is characterized in that the hyperbranched polymer viscosity reducer accounts for 0.01 wt% -2 wt% of the total solid content of the admixture.
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