CN114751671A - Preparation method of polycarboxylic acid admixture for machine-made sand high-strength concrete - Google Patents

Preparation method of polycarboxylic acid admixture for machine-made sand high-strength concrete Download PDF

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CN114751671A
CN114751671A CN202210362584.1A CN202210362584A CN114751671A CN 114751671 A CN114751671 A CN 114751671A CN 202210362584 A CN202210362584 A CN 202210362584A CN 114751671 A CN114751671 A CN 114751671A
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temperature
solution
mother liquor
macromonomer
water
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叶鸿宏
马正林
李官勇
樊兴波
陈芝轩
王伟
罗顺江
魏家旭
胡俊
李白雨
史晓飞
刘睿迪
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Yunnan Construction and Investment Holding Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • C04B40/0046Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular 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

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Abstract

The invention discloses a preparation method of a polycarboxylic acid admixture for machine-made sand high-strength concrete, which comprises the following components in percentage by weight: 16.0-18.0% of polycarboxylic acid high-performance water-reducing mother liquor, 30.0-32.0% of six-carbon comprehensive mother liquor, 38.0-40.0% of polycarboxylic acid high-performance slump retaining mother liquor, 4.0-6.0% of sodium gluconate, 4.0-10.0% of white sugar and 7 of 740 ten-thousandth of defoaming ten-thousandth.

Description

Preparation method of polycarboxylic acid admixture for machine-made sand high-strength concrete
Technical Field
The invention relates to the field of building material concrete, and particularly provides a preparation method of a machine-made sand high-strength concrete polycarboxylic admixture.
Background
The super high-rise pumped concrete mixing ratio design technology is a modern concrete pumping technology with the pumping height of more than 100 m. With the expansion of urbanization process, super high-rise buildings are more and more, the design technology of the mix proportion of pumping concrete for the super high-rise buildings becomes an indispensable key of the construction technology of the super high-rise buildings, and for the pumping concrete for the super high-rise buildings with the height of more than 300m, the pumping concrete for pumping high strength has high pressure and high viscosity, and the pumping construction is particularly difficult, thereby generating a series of construction technical problems to be solved urgently. Therefore, the research on the super high-rise pumping technology of the high-strength concrete has particularly important practical significance and practical value for the construction quality and the construction efficiency of super high-rise buildings. High-strength and high-performance concrete is increasingly applied to some key projects and civil engineering and construction in China due to the characteristics of high integrity, good durability and the like. At present, the strength of high-strength and high-performance concrete is improved mainly by methods of reducing the water cement ratio, increasing the using amount of cementing materials, preferably selecting fine sand, stone and the like, but the viscosity of the concrete is increased and the fluidity of the concrete is reduced, so that the pumpability of the concrete is reduced, the construction efficiency is greatly reduced, and particularly for ultrahigh-pumping high-strength concrete needing ultrahigh-layer pumping, the popularization and the application of the ultrahigh-pumping high-strength concrete in the field of ultrahigh layers are greatly limited.
In order to solve the problems of high viscosity, poor fluidity and the like of ultra-high-strength concrete mixtures, two methods are mainly adopted at present: the first method is to mix superfine powder such as superfine mineral powder, silica fume, micro-beads and the like, optimize the grading of the rubber material particles to reduce the viscosity of the concrete, but the addition of the superfine powder can greatly increase the cost of the concrete, and simultaneously, the viscosity reduction effect on the ultra-high strength concrete can not completely meet the requirement; and the second method adopts a viscosity-reducing additive, so that the slump loss prevention time of the concrete mixture cannot be ensured.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the polycarboxylic acid admixture for the machine-made sand high-strength concrete is provided, and aims to solve the problems that in the prior art, the water demand rate of the prepared concrete is high and the prepared concrete is easy to separate due to the influence of polyhedral prisms, rough surface appearance and high content of base powder, and solve the problems of overlarge viscosity, small fluidity, large fluidity loss and the like of the existing ultra-high-strength concrete caused by low water-cement ratio and large mixing amount of cement materials.
The technical scheme of the invention is as follows: a preparation method of polycarboxylic acid admixture for machine-made sand high-strength concrete comprises the following steps,
step one, polycarboxylic acid high-performance water-reducing mother liquor
1.1, injecting deionized water with the temperature of 25-35 ℃ into a material melting kettle, adding a isopentenyl polyoxyethylene ether macromonomer, and starting a stirrer to stir and dissolve;
1.2, after the prenyl polyoxyethylene ether macromonomer in the material dissolving kettle is completely dissolved, pumping the polyethylene glycol monomethyl ether esterified macromonomer into the reaction kettle, ensuring that the temperature in the reaction kettle is controlled between 20 and 32 ℃ when the dropwise addition is started, and controlling the temperature of the reaction kettle to be between 50 and 58 ℃ when the mother solution is synthesized;
1.3, adding hydrogen peroxide into a reaction kettle, dropwise adding the solution A at a constant speed for two minutes, dropwise adding the solution B at a constant speed, ensuring that the solution A is completely added within 3 hours, the solution B is completely added within 2.5 hours, controlling the material temperature to be 40-42 ℃ and the dropwise adding speed in the process of dropwise adding A, B solution, preserving heat for 1-2.5 hours after the dropwise adding is completed, adding a sodium hydroxide solution after the heat preservation is completed, and controlling the pH value to be 6-8.5 to obtain a polycarboxylic acid high-performance water-reducing mother liquor, which is marked as PC-1;
step two, preparing six-carbon comprehensive mother liquor:
2.1, injecting deionized water with the temperature of 20-25 ℃ into the material melting kettle, adding a polyether macromonomer and a polyoxyethylene ether macromonomer, and starting a stirrer to stir and dissolve;
2.2, after monomers in the material dissolving kettle are completely dissolved, pumping acrylic acid into a reaction kettle, then adding an initiator and a chain transfer agent in a dropwise manner for 30-50min, keeping the temperature for 2.0h after adding, ensuring that the temperature of materials in the reaction kettle is 18-20 ℃ before adding, the temperature of the materials in the dropwise process is 20-25 ℃, keeping the temperature for about 2h at 20-25 ℃ after finishing adding, adding NaOH after finishing keeping the temperature, adjusting the pH value to be neutral, and then stirring for 30min to obtain the functional mother liquor after finishing reaction; is marked as PC-2;
step three: polycarboxylic acid high-performance slump-retaining mother liquor
3.1 injecting deionized water with the temperature of 25-30 ℃ into a material dissolving kettle, adding methallyl alcohol polyoxyethylene ether, marking as HPEG, starting a stirrer to stir and dissolve, after stirring uniformly, simultaneously dripping deionized water for 2-4h and methallyl polyoxyethylene ether VPEG for 2.5-4h into the reaction kettle, continuously stirring while dripping, preserving heat for 1-2h after dripping, adding sodium hydroxide solution after preserving heat, controlling the pH value to be 6-8, and controlling the mass ratio of the deionized water to the methallyl polyoxyethylene ether VPEG to be 1:0.06-1: 0.08;
3.2 adding an initiator and an initiation aid into the solution obtained in the step 3.1, and stirring for 2min at 23-25 ℃;
3.3 dissolving acrylic acid, hydroxyethyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid in water to obtain a mixed aqueous solution C; dissolving a chain transfer agent in water to obtain a chain transfer agent aqueous solution;
3.4, simultaneously dripping the mixed aqueous solution C and the chain transfer agent aqueous solution into the solution obtained in the step 3.2, and finishing dripping within 1 hour;
3.5, preserving heat for 0.5h after the dropwise addition is finished, adjusting the pH value to 6-7.5 by adopting a sodium hydroxide solution, and adding water to dilute until the solid content is 40%, wherein the mark is PC-3;
step four: mixing the polycarboxylic acid high-performance water-reducing mother liquor PC-1 obtained in the step one, the six-carbon comprehensive mother liquor PC-2 obtained in the step two, the polycarboxylic acid high-performance slump-retaining mother liquor PC-3, a retarder and a defoaming agent in percentage by mass:
Figure BDA0003585688050000031
compounding to form a polycarboxylic acid admixture for machine-made sand high-strength concrete meeting the requirement of ultra-high-rise pumping;
further, in the step one, the solution A is an aqueous solution of acrylic acid and ionized water, the solution B is an aqueous solution of vitamin C and mercaptoacetic acid mixed according to the proportion of 1:1-1:10, the mass ratio of the prenyl polyoxyethylene ether macromonomer to acrylic acid or methacrylic acid is 1:0.08-1:0.26, and the polyethylene glycol monomethyl ether esterified macromonomer is an industrial grade aqueous solution with the relative molecular mass of 500.
Further, in the second step, the polyether macromonomer is 3500-4000 molecular weight monomer and is a mixture of vinyl ether 2+2 and 2+4 type macromonomer, wherein the vinyl ether 2+2 type macromonomer is ethylene glycol monovinyl polyethylene glycol ether and is marked as EPEG; the vinyl ether 2+4 type macromonomer is methyl allyl polyoxyethylene ether and is marked as VPEG; the molar ratio of polyether macromonomer to acrylic acid is 1: 3.
Further, in the second step, the initiator is one or a mixture of two of sodium hypophosphite, ammonium persulfate and sodium methallyl sulfonate.
Further, in the second step, the chain transfer agent is one or a mixture of aliphatic mercaptan and dodecyl mercaptan, and the chain transfer agent: the mass concentration of aliphatic mercaptan is more than 25 percent, and the mass concentration of dodecyl mercaptan is more than 30 percent.
Further, in the second step, the mass fraction ratio of the polyether macromonomer, the initiator and the chain transfer agent to the total of the three is 70-90: 5-20: 5-10.
Further, in the third step, the initiation assistant is one or more of phenolic resin, polyurethane, urea resin, melamine resin, furfural resin and unsaturated polyester resin.
Further, in the third step, the chain transfer agent is one or more of mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, sodium methallylsulfonate and dodecyl mercaptan;
further, in the third step, the initiator is one or more of hydrogen peroxide with the concentration of 27.5%, sodium persulfate, ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
Further, in the fourth step, the water reducing rate of the polycarboxylic acid high-performance water reducing mother liquor is more than or equal to 40%, the water reducing rate of the six-carbon comprehensive mother liquor is more than or equal to 30%, the water reducing rate of the polycarboxylic acid high-performance slump retaining mother liquor is more than or equal to 20%, the retarder is a mixture of sodium gluconate and white sugar, and the defoamer is 740 defoamer.
The invention has the following beneficial effects: compared with the prior art, the method has the advantages that,
the idea of the invention is to use dicarboxylic acid polymerization monomer to partially replace the traditional monocarboxylic acid functional monomer, the mother liquor adopts a low-temperature control process in the production process, the reactivity ratio of EPEG and VPEG type monomers and acrylic small monomers in the low-temperature production process is more efficient, the reaction is closer to ideal constant ratio copolymerization and the reaction process is easier to control, meanwhile, the anchoring effect of adsorptive groups on the surfaces of different particles is enhanced under the low-temperature production, the steric hindrance of long side chains in a liquid phase is improved, the flocculation probability between cement particles is reduced, and the dispersion performance between the particles is improved, so that the flow performance of the concrete mixture is further improved; the six-carbon comprehensive mother liquor and the polycarboxylic acid high-performance slump-retaining mother liquor are beneficial to the composition synthesis of the slump-retaining mother liquor in low-temperature synthesis, and meanwhile, the conversion rate can be improved by the VPEG variable-speed dropping process, the molecular weight is low, and the effective components of the water reducer are very high, so that the initial dispersing capacity is high, and the slump-retaining dispersion retaining capacity is excellent; when the variety and fineness of cement are changed and the mud content of coarse and fine aggregates fluctuates greatly, ordinary polycarboxylic acid can not adapt. In order to meet the process requirement and optimize the mixing amount, raw materials on a construction site are better used for trial distribution, the overall water reducing and slump retaining performance of the mother liquor produced by low-temperature synthesis is more efficient than that of the common mother liquor, and the mother liquor is more suitable for the change of cement types, fineness, and the mud content and gradation of coarse and fine aggregates.
1. The polycarboxylic admixture effectively overcomes the inherent defects of poor gradation of machine-made sand and rough surface appearance, and solves the problems of large water requirement, segregation and the like of concrete prepared by using machine-made sand in the prior art;
2. the water-cement ratio of the invention is W/C0.21, and the polycarboxylic admixture prepared by the invention effectively improves the problems of concrete viscosity increase, fluidity reduction and the like of the existing ultra-high strength concrete caused by low water-cement ratio and large amount of gelled materials.
3. The polycarboxylic acid admixture effectively solves the problem of large slump loss, can ensure that the slump loss of concrete for 4 hours is almost zero by using the polycarboxylic acid admixture, greatly reduces the return rate of the concrete, reduces the consumption of the admixture on the premise of ensuring the quality of the concrete, reduces the stirring resistance of equipment and the wear rate of the equipment, shortens the stirring time and the power consumption of the concrete, improves the utilization rate of the equipment and a transportation tank car, and reduces the cost of the oil consumption tank car caused by the return of the concrete.
Detailed Description
In order to make the contents, technical solutions and advantages of the present invention more apparent, the present invention is further illustrated below with reference to specific examples, which are only used for illustrating the present invention, and the present invention is not limited to the following examples.
The machine-made sand C110 ultra-high pumping high-strength concrete polycarboxylic admixture comprises the following components in parts by mass:
example 1:
(1) preparation of PC-1: injecting deionized water with the temperature of 25-35 ℃ into the material melting kettle, adding the isopentenyl polyoxyethylene ether macromonomer, and starting a stirrer to stir and dissolve; after the prenyl polyoxyethylene ether macromonomer in the material melting kettle is completely dissolved, pumping the polyethylene glycol monomethyl ether esterified macromonomer into the reaction kettle, ensuring that the temperature in the reaction kettle is controlled between 20 and 32 ℃ when the dropwise addition is started, and controlling the temperature of the reaction kettle to be between 50 and 58 ℃ when the mother solution is synthesized; adding hydrogen peroxide into a reaction kettle, dropwise adding the solution A at a constant speed for two minutes, dropwise adding the solution B at a constant speed, ensuring that the solution A is completely added within 3 hours, the solution B is completely added within 2.5 hours, controlling the material temperature to be 40-42 ℃ and the dropwise adding speed in the process of dropwise adding A, B solution, preserving heat for 1-2.5 hours after dropwise adding, adding a sodium hydroxide solution after preserving heat, and controlling the pH value to be 6-8.5 to obtain a PC-1 mother solution;
(2) preparation of PC-2: injecting deionized water with the temperature of 20-25 ℃ into the material melting kettle, adding polyether macromonomer and polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve; after monomers in the material dissolving kettle are completely dissolved, pumping acrylic acid into a reaction kettle, then adding an initiator and a chain transfer agent in a dropwise manner for 30-50min, preserving heat for 2.0h after dropwise addition, ensuring that the temperature of materials in the reaction kettle is 18-20 ℃ before dropwise addition, the temperature of the materials in the dropwise addition process is 20-25 ℃, keeping the temperature of 20-25 ℃ for about 2h after dropwise addition, adding NaOH after heat preservation, adjusting the pH value to be neutral, and then stirring for 30min to obtain a functional mother solution after reaction, thus obtaining a PC-1 mother solution; wherein, in the preparation of PC-2, the polyether macromonomer is 3500-4000 molecular weight monomer and is a mixture of vinyl ether 2+2 and 2+4 type macromonomers, wherein the vinyl ether 2+2 type macromonomer is ethylene glycol monovinyl polyethylene glycol ether and is marked as EPEG; the vinyl ether 2+4 type macromonomer is methyl allyl polyoxyethylene ether and is marked as VPEG; wherein the mass ratio of the EPEG to the VPEG is 0.1: 0.9, and the molar ratio of the polyether macromonomer to the acrylic acid is 1: 3;
(3) preparation of PC-3: injecting deionized water with the temperature of 25-30 ℃ into a material dissolving kettle, adding methallyl alcohol polyoxyethylene ether, namely HPEG, starting a stirrer to stir and dissolve, after stirring uniformly, dropwise adding deionized water for 2-4h and methallyl polyoxyethylene ether VPEG for 2.5-4h simultaneously into the reaction kettle, continuously stirring while dropwise adding, preserving heat for 1-2h after dropwise adding, adding a sodium hydroxide solution after finishing preserving heat, controlling the pH value to be 6-8, and controlling the mass ratio of the deionized water to the methallyl polyoxyethylene ether VPEG to be 1:0.06-1: 0.08; adding initiator and initiating assistant, and stirring at 23-25 deg.C for 2 min; dissolving acrylic acid, hydroxyethyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid in water to obtain a mixed aqueous solution C; dissolving a chain transfer agent in water to obtain a chain transfer agent aqueous solution; then simultaneously dripping the mixed aqueous solution C and the chain transfer agent aqueous solution for 1 hour; and (3) after the dropwise addition is finished, preserving the heat for 0.5h, adjusting the pH value to 6-7.5 by adopting a sodium hydroxide solution, and adding water to dilute until the solid content is 40%, wherein the mark is PC-3.
Example 2:
(1) preparation of PC-1: injecting deionized water with the temperature of 25-35 ℃ into the material melting kettle, adding the isopentenyl polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve; after the prenyl polyoxyethylene ether macromonomer in the material melting kettle is completely dissolved, pumping the polyethylene glycol monomethyl ether esterified macromonomer into the reaction kettle, ensuring that the temperature in the reaction kettle is controlled between 20 and 32 ℃ when the dropwise addition is started, and controlling the temperature of the reaction kettle to be between 50 and 58 ℃ when mother liquor is synthesized; adding hydrogen peroxide into a reaction kettle, dropwise adding the solution A at a constant speed for two minutes, dropwise adding the solution B at a constant speed, ensuring that the solution A is completely added within 3 hours, the solution B is completely added within 2.5 hours, controlling the temperature of the material to be 40-42 ℃ and the dropwise adding speed in the process of dropwise adding A, B solution, preserving heat for 1-2.5 hours after dropwise adding, adding a sodium hydroxide solution after preserving heat, and controlling the pH value to be 6-8.5 to obtain a PC-1 mother solution;
(2) preparation of PC-2: injecting deionized water with the temperature of 20-25 ℃ into the material melting kettle, adding polyether macromonomer and polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve; after monomers in the material dissolving kettle are completely dissolved, pumping acrylic acid into a reaction kettle, then adding an initiator and a chain transfer agent in a dropwise manner for 30-50min, preserving heat for 2.0h after dropwise addition, ensuring that the temperature of materials in the reaction kettle is 18-20 ℃ before dropwise addition, the temperature of the materials in the dropwise addition process is 20-25 ℃, keeping the temperature of 20-25 ℃ for about 2h after dropwise addition, adding NaOH after heat preservation, adjusting the pH value to be neutral, and then stirring for 30min to obtain a functional mother solution after reaction, thus obtaining a PC-1 mother solution; wherein, in the preparation of PC-2, the polyether macromonomer is 3500-4000 molecular weight monomer and is a mixture of vinyl ether 2+2 and 2+4 type macromonomers, wherein the vinyl ether 2+2 type macromonomer is ethylene glycol monovinyl polyethylene glycol ether and is marked as EPEG; the vinyl ether 2+4 type macromonomer is methyl allyl polyoxyethylene ether and is marked as VPEG; wherein the weight ratio of the EPEG to the VPEG is 0.1: 0.9, and the molar ratio of the polyether macromonomer to the acrylic acid is 1: 3;
(3) preparation of PC-3: injecting deionized water with the temperature of 25-30 ℃ into a material dissolving kettle, adding methallyl alcohol polyoxyethylene ether, namely HPEG, starting a stirrer to stir and dissolve, after stirring uniformly, dropwise adding deionized water for 2-4h and methallyl polyoxyethylene ether VPEG for 2.5-4h simultaneously into the reaction kettle, continuously stirring while dropwise adding, preserving heat for 1-2h after dropwise adding, adding a sodium hydroxide solution after finishing preserving heat, controlling the pH value to be 6-8, and controlling the mass ratio of the deionized water to the methallyl polyoxyethylene ether VPEG to be 1:0.06-1: 0.08; adding initiator and initiating assistant, and stirring at 23-25 deg.C for 2 min; dissolving acrylic acid, hydroxyethyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid in water to obtain a mixed aqueous solution C; dissolving a chain transfer agent in water to obtain a chain transfer agent aqueous solution; then simultaneously dripping the mixed aqueous solution C and the chain transfer agent aqueous solution for 1 hour; and (3) after the dropwise addition is finished, preserving the heat for 0.5h, adjusting the pH value to 6-7.5 by adopting a sodium hydroxide solution, and adding water to dilute until the solid content is 40%, wherein the mark is PC-3.
Example 3:
(1) preparation of PC-1: injecting deionized water with the temperature of 25-35 ℃ into the material melting kettle, adding the isopentenyl polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve; after the prenyl polyoxyethylene ether macromonomer in the material melting kettle is completely dissolved, pumping the polyethylene glycol monomethyl ether esterified macromonomer into the reaction kettle, ensuring that the temperature in the reaction kettle is controlled between 20 and 32 ℃ when the dropwise addition is started, and controlling the temperature of the reaction kettle to be between 50 and 58 ℃ when the mother solution is synthesized; adding hydrogen peroxide into a reaction kettle, dropwise adding the solution A at a constant speed for two minutes, dropwise adding the solution B at a constant speed, ensuring that the solution A is completely added within 3 hours, the solution B is completely added within 2.5 hours, controlling the material temperature to be 40-42 ℃ and the dropwise adding speed in the process of dropwise adding A, B solution, preserving heat for 1-2.5 hours after dropwise adding, adding a sodium hydroxide solution after preserving heat, and controlling the pH value to be 6-8.5 to obtain a PC-1 mother solution;
(2) preparation of PC-2: injecting deionized water with the temperature of 20-25 ℃ into the material melting kettle, adding polyether macromonomer and polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve; after monomers in the material dissolving kettle are completely dissolved, pumping acrylic acid into a reaction kettle, then adding an initiator and a chain transfer agent in a dropwise manner for 30-50min, preserving heat for 2.0h after dropwise addition, ensuring that the temperature of materials in the reaction kettle is 18-20 ℃ before dropwise addition, the temperature of the materials in the dropwise addition process is 20-25 ℃, keeping the temperature of 20-25 ℃ for about 2h after dropwise addition, adding NaOH after heat preservation, adjusting the pH value to be neutral, and then stirring for 30min to obtain a functional mother solution after reaction, thus obtaining a PC-1 mother solution; wherein, in the preparation of PC-2, the polyether macromonomer is 3500-4000 molecular weight monomer and is a mixture of vinyl ether 2+2 and 2+4 type macromonomers, wherein the vinyl ether 2+2 type macromonomer is ethylene glycol monovinyl polyethylene glycol ether and is marked as EPEG; the vinyl ether 2+4 type macromonomer is methyl allyl polyoxyethylene ether and is marked as VPEG; wherein the mass ratio of the EPEG to the VPEG is 0.05: 0.95, and the molar ratio of the polyether macromonomer to the acrylic acid is 1: 3;
(3) preparation of PC-3: injecting deionized water with the temperature of 25-30 ℃ into a material dissolving kettle, adding methallyl alcohol polyoxyethylene ether, marked as HPEG, starting a stirrer to stir and dissolve, after stirring uniformly, dropwise adding deionized water for 2-4h and methallyl polyoxyethylene ether VPEG for 2.5-4h into the reaction kettle simultaneously, continuously stirring while dropwise adding, keeping the temperature for 1-2h after dropwise adding is finished, adding a sodium hydroxide solution after the temperature is kept, controlling the pH value to be 6-8, and controlling the mass ratio of the deionized water to the methallyl polyoxyethylene ether VPEG to be 1:0.06-1: 0.08; adding initiator and initiating assistant, and stirring at 23-25 deg.C for 2 min; dissolving acrylic acid, hydroxyethyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid in water to obtain a mixed aqueous solution C; dissolving a chain transfer agent in water to obtain a chain transfer agent aqueous solution; then simultaneously dripping the mixed aqueous solution C and the chain transfer agent aqueous solution for 1 hour; and (3) after the dropwise addition is finished, preserving the heat for 0.5h, adjusting the pH value to 6-7.5 by adopting a sodium hydroxide solution, and adding water to dilute until the solid content is 40%, wherein the mark is PC-3.
Example 4:
(1) preparation of PC-1: injecting deionized water with the temperature of 25-35 ℃ into the material melting kettle, adding the isopentenyl polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve; after the prenyl polyoxyethylene ether macromonomer in the material melting kettle is completely dissolved, pumping the polyethylene glycol monomethyl ether esterified macromonomer into the reaction kettle, ensuring that the temperature in the reaction kettle is controlled between 20 and 32 ℃ when the dropwise addition is started, and controlling the temperature of the reaction kettle to be between 50 and 58 ℃ when the mother solution is synthesized; adding hydrogen peroxide into a reaction kettle, dropwise adding the solution A at a constant speed for two minutes, dropwise adding the solution B at a constant speed, ensuring that the solution A is completely added within 3 hours, the solution B is completely added within 2.5 hours, controlling the material temperature to be 40-42 ℃ and the dropwise adding speed in the process of dropwise adding A, B solution, preserving heat for 1-2.5 hours after dropwise adding, adding a sodium hydroxide solution after preserving heat, and controlling the pH value to be 6-8.5 to obtain a PC-1 mother solution;
(2) preparation of PC-2: injecting deionized water with the temperature of 20-25 ℃ into the material melting kettle, adding polyether macromonomer and polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve; after monomers in the material dissolving kettle are completely dissolved, pumping acrylic acid into a reaction kettle, then adding an initiator and a chain transfer agent in a dropwise manner for 30-50min, preserving heat for 2.0h after dropwise addition, ensuring that the temperature of materials in the reaction kettle is 18-20 ℃ before dropwise addition, the temperature of the materials in the dropwise addition process is 20-25 ℃, keeping the temperature of 20-25 ℃ for about 2h after dropwise addition, adding NaOH after heat preservation, adjusting the pH value to be neutral, and then stirring for 30min to obtain a functional mother solution after reaction, thus obtaining a PC-1 mother solution; wherein, in the preparation of PC-2, the polyether macromonomer is 3500-4000 molecular weight monomer and is a mixture of vinyl ether 2+2 and 2+4 type macromonomers, wherein the vinyl ether 2+2 type macromonomer is ethylene glycol monovinyl polyethylene glycol ether and is marked as EPEG; the vinyl ether 2+4 type macromonomer is methyl allyl polyoxyethylene ether and is marked as VPEG; wherein the mass ratio of the EPEG to the VPEG is 0.05: 0.95, and the molar ratio of the polyether macromonomer to the acrylic acid is 1: 3;
(3) preparation of PC-3: injecting deionized water with the temperature of 25-30 ℃ into a material dissolving kettle, adding methallyl alcohol polyoxyethylene ether, namely HPEG, starting a stirrer to stir and dissolve, after stirring uniformly, dropwise adding deionized water for 2-4h and methallyl polyoxyethylene ether VPEG for 2.5-4h simultaneously into the reaction kettle, continuously stirring while dropwise adding, preserving heat for 1-2h after dropwise adding, adding a sodium hydroxide solution after finishing preserving heat, controlling the pH value to be 6-8, and controlling the mass ratio of the deionized water to the methallyl polyoxyethylene ether VPEG to be 1:0.06-1: 0.08; adding initiator and initiating assistant, and stirring at 23-25 deg.C for 2 min; dissolving acrylic acid, hydroxyethyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid in water to obtain a mixed aqueous solution C; dissolving a chain transfer agent in water to obtain a chain transfer agent aqueous solution; then simultaneously dripping the mixed aqueous solution C and the chain transfer agent aqueous solution for 1 hour; and (3) after the dropwise addition is finished, preserving the heat for 0.5h, adjusting the pH value to 6-7.5 by adopting a sodium hydroxide solution, and adding water to dilute until the solid content is 40%, wherein the mark is PC-3.
The compound weight percentage of the admixture is shown in the following table:
Figure BDA0003585688050000091
the following experiments were carried out according to the compounding ratios of the above compounded admixtures:
the mass ratio of the experimental components is as follows:
kind of raw material Cement (52.5) Mineral powder (S115) Silica fume Microbeads Sand Stone (stone) Water (W) Additive agent
Single dosage (Kg/m)3) 580 40 60 120 600 10000 165 8.7
The cement is 52.5 cement with a specific surface area of 350Kg/m3The density is 3100Kg/m3The 28d mortar has the strength of 56.8MPa, and the stability and the setting time are qualified; the ore powder is S115 iron ore powder with a specific surface area of 420m2Kg, 115% activity index, density 2810m2Per kg; the specific surface area of the silicon ash is 15000-2Per kg, 120% activity index, 2400m density2Per kg; the micro-beads are fly ash micro-beads with the specific surface area of 400m2Per kg, 95% activity index, 2400m density2Per kg; the sand is machine-made sand, the fineness modulus is 2.9, the content of the base powder is 12.5 percent, the MB value is 0.5, and the MB value is a sub-blue value and represents the mud content in the machine-made sand. The crushed stone with the particle size of 5-10mm and the crushed stone with the particle size of 10-20mm are used in a composite mode according to the proportion of 0.30: 0.70, and the mud content is 0.1%. The polycarboxylic acid admixture is the admixture of the present invention.
The workability test is carried out according to GB/T50080-2002 Standard of common concrete mixture Performance test methods, the concrete test block is taken as a reference object, and a universal pressure tester is used for testing the compressive strength of the embodiment according to GB/T50081-2002 Standard of common concrete mechanical Performance test methods.
TABLE 1 results of workability test of concrete
Figure BDA0003585688050000101
TABLE 2 concrete compressive Strength test results
7d compressive Strength (MPa) 28d compressive Strength (MPa)
Example 1 110.2 123.2
Example 2 115.5 125.2
Example 3 107.5 124.3
Example 4 108.1 134.0
From the above tables 1 and 2, it can be seen that the polycarboxylic acid admixture obtained by the invention has the characteristics of high fluidity, low viscosity and the like under the condition that the concrete compressive strength reaches the standard, and completely meets the requirements of the construction performance and the later strength of the ultra-high strength concrete.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments and it is not intended to limit the invention to the specific embodiments described. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (10)

1. A preparation method of polycarboxylic acid admixture for machine-made sand high-strength concrete is characterized by comprising the following steps,
step one, polycarboxylic acid high-performance water-reducing mother liquor
1.1, injecting deionized water with the temperature of 25-35 ℃ into a material melting kettle, adding a prenyl polyoxyethylene ether macromonomer, starting a stirrer to stir and dissolve;
1.2, after the prenyl polyoxyethylene ether macromonomer in the material dissolving kettle is completely dissolved, pumping the polyethylene glycol monomethyl ether esterified macromonomer into the reaction kettle, ensuring that the temperature in the reaction kettle is controlled between 20 and 32 ℃ when the dropwise addition is started, and controlling the temperature of the reaction kettle to be between 50 and 58 ℃ when the mother solution is synthesized;
1.3, adding hydrogen peroxide into a reaction kettle, dropwise adding the solution A at a constant speed for two minutes, dropwise adding the solution B at a constant speed, ensuring that the solution A is completely added within 3 hours, the solution B is completely added within 2.5 hours, controlling the material temperature to be 40-42 ℃ and the dropwise adding speed in the process of dropwise adding A, B solution, preserving heat for 1-2.5 hours after the dropwise adding is completed, adding a sodium hydroxide solution after the heat preservation is completed, and controlling the pH value to be 6-8.5 to obtain a polycarboxylic acid high-performance water-reducing mother liquor, which is marked as PC-1;
step two, preparing six-carbon comprehensive mother liquor:
2.1, injecting deionized water with the temperature of 20-25 ℃ into the material melting kettle, adding a polyether macromonomer and a polyoxyethylene ether macromonomer, and starting a stirrer to stir and dissolve;
2.2, after monomers in the material melting kettle are completely dissolved, pumping acrylic acid into a reaction kettle, then dropwise adding an initiator and a chain transfer agent for 30-50min, keeping the temperature for 2.0h after dropwise adding, ensuring that the temperature of materials in the reaction kettle is 18-20 ℃ before dropwise adding, the temperature of the materials in the dropwise adding process is 20-25 ℃, keeping the temperature for about 2h at 20-25 ℃ after dropwise adding is finished, adding NaOH after the temperature is kept, adjusting the pH value to be neutral, and then stirring for 30min to obtain the functional mother liquor after reaction; is marked as PC-2;
step three: polycarboxylic acid high-performance slump retaining mother liquor
3.1, injecting deionized water with the temperature of 25-30 ℃ into a material dissolving kettle, adding methallyl alcohol polyoxyethylene ether, namely HPEG, starting a stirrer to stir and dissolve, after stirring uniformly, dropwise adding deionized water for 2-4h and methallyl polyoxyethylene ether VPEG for 2.5-4h into the reaction kettle simultaneously, continuously stirring while dropwise adding, keeping the temperature for 1-2h after dropwise adding is finished, adding a sodium hydroxide solution after the temperature is kept, controlling the pH value to be 6-8, and controlling the mass ratio of the deionized water to the methallyl polyoxyethylene ether VPEG to be 1:0.06-1: 0.08;
3.2 adding an initiator and an initiation aid into the solution obtained in the step 3.1, and stirring for 2min at 23-25 ℃;
3.3 dissolving acrylic acid, hydroxyethyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid in water to obtain a mixed aqueous solution C; dissolving a chain transfer agent in water to obtain a chain transfer agent aqueous solution;
3.4, simultaneously dripping the mixed aqueous solution C and the chain transfer agent aqueous solution into the solution obtained in the step 3.2, and finishing dripping within 1 hour;
3.5, preserving heat for 0.5h after the dropwise addition is finished, adjusting the pH value to 6-7.5 by adopting a sodium hydroxide solution, and adding water to dilute until the solid content is 40%, wherein the mark is PC-3;
step four: mixing the polycarboxylic acid high-performance water-reducing mother liquor PC-1 obtained in the step one, the six-carbon comprehensive mother liquor PC-2 obtained in the step two, the polycarboxylic acid high-performance slump-retaining mother liquor PC-3, a retarder and a defoaming agent in percentage by mass:
16.0 to 18.0 percent of polycarboxylic acid high-performance water-reducing mother liquor
30.0 to 32.0 percent of six-carbon comprehensive mother liquor
38.0 to 40.0 percent of polycarboxylic acid high-performance slump-retaining mother liquor
8.0 to 16.0 percent of retarder
6 to 7 parts per million of the antifoaming agent
And compounding to form the polycarboxylic acid admixture for the machine-made sand high-strength concrete meeting the requirement of ultra-high-rise pumping.
2. The preparation method according to claim 1, wherein the solution A in the step one is an aqueous solution of acrylic acid and ionized water, the solution B is an aqueous solution of vitamin C and mercaptoacetic acid mixed in a ratio of 1:1-1:10, the mass ratio of the prenyl polyoxyethylene ether macromonomer to acrylic acid or methacrylic acid is 1:0.08-1:0.26, and the polyethylene glycol monomethyl ether esterified macromonomer is technical grade, and has a relative molecular mass of 500.
3. The preparation method as claimed in claim 1, wherein the polyether macromonomer in step two is 3500-4000 molecular weight monomer, and is a mixture of vinyl ether 2+2 and 2+4 type macromonomers, wherein the vinyl ether 2+2 type macromonomer is ethylene glycol monovinyl polyethylene glycol ether, denoted as EPEG; the vinyl ether 2+4 type macromonomer is methyl allyl polyoxyethylene ether and is marked as VPEG; the molar ratio of polyether macromonomer to acrylic acid is 1: 3.
4. The preparation method according to claim 1, wherein the initiator in the second step is one or a mixture of two of sodium hypophosphite, ammonium persulfate and sodium methallyl sulfonate.
5. The preparation method according to claim 1, wherein the chain transfer agent in the second step is one or a mixture of aliphatic mercaptan and dodecyl mercaptan, and the chain transfer agent: the mass concentration of aliphatic mercaptan is more than 25 percent, and the mass concentration of dodecyl mercaptan is more than 30 percent.
6. The preparation method of claim 1, wherein the mass fraction ratio of the polyether macromonomer, the initiator and the chain transfer agent in the second step to the total of the three components is 70-90: 5-20: 5-10.
7. The preparation method of claim 1, wherein the initiation additive in step three is one or more of phenolic resin, polyurethane, urea-formaldehyde resin, melamine-formaldehyde resin, furfural resin and unsaturated polyester resin.
8. The preparation method of claim 1, wherein the chain transfer agent in step three is one or more of mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, sodium methallyl sulfonate and dodecyl mercaptan.
9. The preparation method according to claim 1, wherein the initiator in step three is one or more of hydrogen peroxide, sodium persulfate, ammonium persulfate, potassium persulfate and azobisisobutyronitrile with the concentration of 27.5%.
10. The preparation method of claim 1, wherein in the fourth step, the water reducing rate of the polycarboxylic acid high-performance water-reducing mother liquor is not less than 40%, the water reducing rate of the six-carbon comprehensive mother liquor is not less than 30%, the water reducing rate of the polycarboxylic acid high-performance slump-retaining mother liquor is not less than 20%, the retarder is a mixture of sodium gluconate and white sugar, and the defoamer is 740 defoamer.
CN202210362584.1A 2022-04-07 2022-04-07 Preparation method of polycarboxylic acid admixture for machine-made sand high-strength concrete Pending CN114751671A (en)

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