WO2022056975A1 - Preparation method for polycarboxylic acid admixture for use in machine-made sand concrete - Google Patents

Preparation method for polycarboxylic acid admixture for use in machine-made sand concrete Download PDF

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WO2022056975A1
WO2022056975A1 PCT/CN2020/120796 CN2020120796W WO2022056975A1 WO 2022056975 A1 WO2022056975 A1 WO 2022056975A1 CN 2020120796 W CN2020120796 W CN 2020120796W WO 2022056975 A1 WO2022056975 A1 WO 2022056975A1
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machine
water
made sand
admixture
concrete
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PCT/CN2020/120796
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French (fr)
Chinese (zh)
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王文军
王道正
雷文晗
陈囡
赵力
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江苏尼高科技有限公司
常州市建筑科学研究院集团股份有限公司
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Publication of WO2022056975A1 publication Critical patent/WO2022056975A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to the field of cement-based concrete admixtures, and is suitable for machine-made sand concrete with severe gradation failure and high stone powder content, in particular to a preparation method of a polycarboxylic acid admixture for machine-made sand concrete.
  • the patent with publication number CN 109627394 A discloses a water reducing agent suitable for machine-made sand concrete and its preparation method. Specifically, isobutenol polyoxyethylene ether, acrylic acid and 2-acrylamido dodecyl sulfonic acid are used as the main reaction units to initiate a free copolymerization reaction under a redox reaction system at 55 to 75 ° C. After the reaction, use A polycarboxylate water reducing agent suitable for machine-made sand concrete can be obtained by neutralizing the organic alkali.
  • the solution provided by this patent is based on the idea of isobutenol polyoxyethylene ether as the main reaction body. Compared with the idea of ethylene glycol monovinyl polyethylene glycol ether (EPEG) monomer, the performance space is limited, the production process is complicated, and the production High energy consumption.
  • EPEG ethylene glycol monovinyl polyethylene glycol ether
  • CN 111153627 A discloses a kind of anti-mud type admixture suitable for machine-made sand concrete and its compound method.
  • the main method is to compound viscosity-reducing polycarboxylate water-reducing agent, lignin water-reducing agent, water and defoamer.
  • This patent mainly describes the combination of viscosity-reducing polycarboxylate water-reducing agent, lignin water-reducing agent and defoaming agent to configure an anti-mud type admixture suitable for machine-made sand concrete.
  • the main raw material of the viscosity-reducing polycarboxylic acid provided in the patent is methacrylic acid-polyethylene glycol methyl ether ester as the main raw material.
  • the production process of this raw material requires a high-temperature esterification process, which has a long production cycle and high energy consumption.
  • the lignosulfonate water reducing agent used in the anti-mud type admixture product has poor resistance to concrete slump loss.
  • the technical problem to be solved by the present invention is: in order to overcome the deficiencies in the prior art, a novel preparation method of a polycarboxylic acid admixture for machine-made sand concrete is provided.
  • the technical scheme adopted in the present invention is: a method for preparing a polycarboxylic acid admixture for machine-made sand concrete, which is characterized in that it comprises the following steps:
  • material preparation ethylene glycol monovinyl polyglycol ether monomer is dissolved in water gained solution as bottom material, acrylic acid, chain transfer agent are dissolved in water gained mixed solution as A material, reducing agent is dissolved in water gained solution as B material;
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, adding the hydrogen peroxide whose mass fraction is 27.5% in the reactor and stirring evenly, then dripping in the reactor Add material A and material B, and the dropwise addition is completed in 1-1.5 hours. After the dropwise addition, the reaction kettle is kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor of step (1) III gained and polyether phosphate, foam control agent, viscosity modifier, water are compounded in proportion at normal temperature, and the mass parts of each material are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained.
  • the ethylene glycol monovinyl polyglycol ether (EPEG) monomer is used as the main synthetic unit and acrylic acid and its derivatives are copolymerized under the action of a redox initiation system to form an anti-mud type water reducing agent with a comb-shaped molecular structure.
  • EPEG ethylene glycol monovinyl polyglycol ether
  • Its concrete water reduction rate is ⁇ 32%; then it can solve the problems of large slump loss and poor material adaptability by compounding with polyether phosphate and organic foam control agent, and can significantly increase the strength of concrete; it can be solved by compounding with concrete viscosity modifier Segregation, bleeding, bottom scraping and other phenomena caused by broken gradation of machine-made sand, fluctuation of stone powder and fluctuation of fine sand and mud content.
  • the molar ratio of the ether group of ethylene glycol monovinyl polyethylene glycol ether in the base material in the step (1) I to the acid group of the acrylic acid in the A material is 3 to 5:1.
  • the solute mass ratio of the bottom material and the A material is 1:0.05-0.15.
  • the molecular weight of ethylene glycol monovinyl polyglycol ether in the bottom material in described step (1) I is 2400, 3000 or 6000.
  • the chain transfer agent in material A is one or a mixture of mercaptopropionic acid and mercaptoacetic acid.
  • the reductant of the B material in the step (1) I is a low-temperature reductant (H001) that can undergo an oxidation-reduction reaction with hydrogen peroxide under a low-temperature condition.
  • the solute mass ratio of hydrogen peroxide and material B is 0.8-2:1.
  • the ratio of the solute mass sum of the base material monomer EPEG to hydrogen peroxide and material B is 100:0.3-0.8.
  • the mud-resistant polycarboxylate water-reducing agent prepared in the step (1) has a concrete water-reducing rate of more than 32%, and has a certain slump-preserving performance.
  • the organic foam control agent in the step (2) is an organic alkynyl alcohol substance, which has the functions of inhibiting the generation of large bubbles in the concrete and introducing tiny bubbles, and can directly replace the traditional silicone, polyether defoamer and air-entraining agent. agent combination.
  • the polyether phosphate in the step (2) is an organic small molecular substance that has a certain effect of retarding setting and slump protection for concrete and can increase the compressive strength.
  • the concrete viscosity modifier in the step (2) is a biopolymeric admixture, which can change the rheological properties of the concrete and has a certain water retention effect, so that the concrete is not easily segregated when using broken graded machine-made sand and contains a lot of stone powder. , bleeding, scraping the bottom and other phenomena.
  • the polycarboxylate water-reducing agent mother liquor synthesized in the present invention takes ethylene glycol monovinyl polyglycol ether (EPEG) monomer as the main raw material and acrylic acid or its derivatives under the action of redox reaction system.
  • EPEG ethylene glycol monovinyl polyglycol ether
  • the polycarboxylate water-reducing agent with comb-shaped molecular structure is formed by the copolymerization of radicals.
  • HPEG isobutenol polyoxyethylene ether
  • TPEG isopentenol polyoxyethylene ether
  • the substitution structure further reduces the steric resistance of the swing of the polyether side chain, making the swing of the polyether side chain more free and the range of activities larger; the increase in the degree of freedom of the swing of the polyether side chain improves the encapsulation and flexibility of the polyether side chain. Therefore, the synthesized polycarboxylate water-reducing agent has better adaptability, especially in the case of poor sand and gravel quality and high mud content.
  • the polyether phosphate selected in the present invention is mainly an organic molecular compound containing a phosphate structure, which has an obvious inhibitory effect on the excessive adsorption of the polycarboxylate water reducing agent by the stone powder and fine sand in the machine-made sand. It controls the slump loss, has a certain dispersing effect on the cement, and can effectively increase the strength of concrete in the middle and late stages.
  • the organic alkynyl alcohol foam control agent in the invention can control the size of air bubbles in concrete, eliminate large air bubbles that have harmful effects on concrete, and leave small air bubbles that can improve the fluidity and durability of concrete, replacing traditional defoamer and Air-entraining agent component; and has good compatibility with polycarboxylate water reducer, and is not easy to cause quality fluctuations due to delamination.
  • the present invention uses EPEG as the main body to synthesize a polycarboxylate water reducing agent with less resistance to the space movement of the polyether side chain and greater degree of freedom, which has better performance in dealing with broken-graded machine-made sand and fine sand with high mud content. effect.
  • polyether phosphate can significantly reduce slump loss and increase strength.
  • organic foam control agent can significantly adjust the bubble structure of concrete, eliminate large bubbles, introduce small bubbles, and improve the fluidity of concrete.
  • the function of concrete viscosity adjusting material is to improve the water retention of concrete and improve the phenomenon of segregation and bleeding.
  • the present invention has the following advantages:
  • the polycarboxylate water-reducing agent prepared by the present invention effectively solves the problems of large concrete slump, poor workability and insufficient strength caused by large content of machine-made sand and gravel powder and broken gradation.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*570mm, 200/510*500mm, 25.5MP, 33.5MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*580mm, 200/510*520mm, 25.0MP, 33.8MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 4.0 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/575*570mm, 190/500*530mm, 26.6MP, 34.5MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/590*580mm, 210/530*520mm, 26.5MP, 35.2MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*580mm, 220/530*550mm, 27.0MP, 36.9MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 240/590*600mm, 220/550*560mm, 28.9MP, 37.8MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*575mm, 200/510*505mm, 25.9MP, 33.8MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*580mm, 200/510*510mm, 26.3MP, 34.7MP.
  • a method for preparing a polycarboxylic acid admixture for machine-made sand concrete comprising the following steps:
  • step II redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5 ⁇ 16 °C, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
  • the anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
  • the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 240/590*610mm, 220/550*570mm, 29.3MP, 38.4MP.
  • the polycarboxylate admixture for machine-made sand concrete prepared by the above examples has high concrete water reduction rate, strong slump resistance resistance and good workability of concrete, and the compressive strength of concrete 7d and 28d is significantly improved.

Abstract

A preparation method for a polycarboxylic acid admixture for use in a machine-made sand concrete, comprising the following steps: (1) preparing a mud-resistant polycarboxylic acid water reducer masterbatch with ethylene-glycol monovinyl polyethylene glycol (EPEG) monomers serving as primary reaction units, and (2) proportionally compounding at room temperature the mud-resistant polycarboxylic acid water reducer masterbatch, a polyether organophosphate, a foam control agent, a concrete viscosity modifier, and water to produce the polycarboxylic acid admixture for use in the machine-made sand concrete. The polycarboxylic acid admixture for use in the machine-made sand concrete has a high water reduction rate, has strong material adaptability, provides enhanced capability in controlling slump loss, and has the effect of suppressing large bubbles in the concrete and improving the workability of the concrete, and, with respect to the machine-made sand concrete that is gap-graded and has a high rock powder content (6-12%), provides the effect of significantly improving workability and enhancing strength.

Description

一种用于机制砂混凝土的聚羧酸外加剂制备方法A kind of preparation method of polycarboxylic acid admixture for machine-made sand concrete 技术领域technical field
本发明属于水泥基混凝土外加剂领域，适用于断级配较严重且石粉含量较高的机制砂混凝土，尤其是一种用于机制砂混凝土的聚羧酸外加剂制备方法。The invention belongs to the field of cement-based concrete admixtures, and is suitable for machine-made sand concrete with severe gradation failure and high stone powder content, in particular to a preparation method of a polycarboxylic acid admixture for machine-made sand concrete.
背景技术Background technique
由于资源紧张的局面越来越得不到缓解，机制砂混凝土近年来作为重要的建筑材料越来越得到广泛应用，由于其断级配现象较严重，且石粉含量高，所拌制的混凝土拌合物粘度高、流动性差、工作性能差，容易产生泌水、离析现象。目前解决这类问题主要方法是通过脂肪族减水剂和萘系减水剂复配适量引气剂，由于脂肪族减水剂和萘系减水剂属于第二代减水剂，不仅生产成本高且容易造成环境污染，虽然具有材料适应性好的优点但是其混凝土减水率低，在配置高性能混凝土时性能往往达不到要求。普通聚羧酸减水剂虽然减水率能达到要求，但是其对石粉含量波动较大的机制砂和含泥量波动较大的细砂适应性较差，往往会引起离析、泌水、扒底等现象，进而影响混凝土的工作性、强度等性能。Due to the shortage of resources that cannot be alleviated more and more, machine-made sand concrete has become more and more widely used as an important building material in recent years. The compound has high viscosity, poor fluidity and poor working performance, and is prone to bleeding and segregation. At present, the main method to solve such problems is to mix an appropriate amount of air-entraining agent with aliphatic water-reducing agent and naphthalene-based water-reducing agent. It is high and easy to cause environmental pollution. Although it has the advantages of good material adaptability, its concrete water reduction rate is low, and its performance often fails to meet the requirements when configuring high-performance concrete. Although the water-reducing rate of ordinary polycarboxylate superplasticizers can meet the requirements, it has poor adaptability to machine-made sand with large fluctuations in stone powder content and fine sand with large fluctuations in mud content, which often causes segregation, bleeding, and scraping. It will affect the workability, strength and other properties of concrete.
如公开号为CN 109627394 A的专利公开了一种适应机制砂混凝土减水剂的及其制备方法。具体利用异丁烯醇聚氧乙烯醚、丙烯酸和2-丙烯酰胺基十二烷基磺酸作为主要反应单元在55～75℃条件下利用氧化还原应发体系下引发进行自由共聚反应，反应结束后利用有机碱中和即得一种适应于机制砂混凝土的聚羧酸减水剂。该专利提供的方案是以异丁烯醇聚氧乙烯醚为反应主体的思路，相对于乙二醇单乙烯基聚乙二醇醚(EPEG)单体的思路，性能空间有限，生产过程复杂，且生产能耗较高。For example, the patent with publication number CN 109627394 A discloses a water reducing agent suitable for machine-made sand concrete and its preparation method. Specifically, isobutenol polyoxyethylene ether, acrylic acid and 2-acrylamido dodecyl sulfonic acid are used as the main reaction units to initiate a free copolymerization reaction under a redox reaction system at 55 to 75 ° C. After the reaction, use A polycarboxylate water reducing agent suitable for machine-made sand concrete can be obtained by neutralizing the organic alkali. The solution provided by this patent is based on the idea of isobutenol polyoxyethylene ether as the main reaction body. Compared with the idea of ethylene glycol monovinyl polyethylene glycol ether (EPEG) monomer, the performance space is limited, the production process is complicated, and the production High energy consumption.
又如公开号为CN 111153627 A的专利公开了一种适应于机制砂混凝土的抗 泥型外加剂及其复配方法。主要方法是将降粘型聚羧酸减水剂、木质素减水剂、水和消泡剂复配而成。通过改变木质素减水剂的质量占比和加入顺序而改变机制砂的性能，与现有技术相比可提高机制砂混凝土的粘聚性和抗压强度。该专利主要描述利用降粘型聚羧酸减水剂、木质素减水剂、消泡剂复合的思路配置适用机制砂混凝土的抗泥型外加剂。专利中提供的降粘型聚羧酸的主要原材料是以甲基丙烯酸-聚乙二醇甲醚酯为主要原材料，该原材料生产过程需经过高温酯化工艺，生产周期长，且能耗较高。且该抗泥型外加剂产品利用的木质素磺酸盐减水剂抵抗混凝土坍落度损失能力差。Another example is the patent of CN 111153627 A, which discloses a kind of anti-mud type admixture suitable for machine-made sand concrete and its compound method. The main method is to compound viscosity-reducing polycarboxylate water-reducing agent, lignin water-reducing agent, water and defoamer. By changing the mass proportion and adding sequence of the lignin water-reducing agent to change the properties of the manufactured sand, the cohesion and compressive strength of the manufactured sand concrete can be improved compared with the prior art. This patent mainly describes the combination of viscosity-reducing polycarboxylate water-reducing agent, lignin water-reducing agent and defoaming agent to configure an anti-mud type admixture suitable for machine-made sand concrete. The main raw material of the viscosity-reducing polycarboxylic acid provided in the patent is methacrylic acid-polyethylene glycol methyl ether ester as the main raw material. The production process of this raw material requires a high-temperature esterification process, which has a long production cycle and high energy consumption. . In addition, the lignosulfonate water reducing agent used in the anti-mud type admixture product has poor resistance to concrete slump loss.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是：为了克服现有技术中存在的不足，提供一种新型的用于机制砂混凝土的聚羧酸外加剂制备方法。The technical problem to be solved by the present invention is: in order to overcome the deficiencies in the prior art, a novel preparation method of a polycarboxylic acid admixture for machine-made sand concrete is provided.
本发明采用的技术方案是：一种用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：包括以下步骤，The technical scheme adopted in the present invention is: a method for preparing a polycarboxylic acid admixture for machine-made sand concrete, which is characterized in that it comprises the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：乙二醇单乙烯基聚乙二醇醚单体溶于水所得溶液作为底料，丙烯酸、链转移剂溶于水所得混合液作为A料，还原剂溶于水所得溶液作为B料；1. material preparation: ethylene glycol monovinyl polyglycol ether monomer is dissolved in water gained solution as bottom material, acrylic acid, chain transfer agent are dissolved in water gained mixed solution as A material, reducing agent is dissolved in water gained solution as B material;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1～1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, adding the hydrogen peroxide whose mass fraction is 27.5% in the reactor and stirring evenly, then dripping in the reactor Add material A and material B, and the dropwise addition is completed in 1-1.5 hours. After the dropwise addition, the reaction kettle is kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液；III. Neutralization: adding lye in the product of step II and adjusting the pH at 5～7.5, and adding water to its solid content is 40%, to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor of step (1) III gained and polyether phosphate, foam control agent, viscosity modifier, water are compounded in proportion at normal temperature, and the mass parts of each material are:
Figure PCTCN2020120796-appb-000001
Figure PCTCN2020120796-appb-000001
即得用于机制砂混凝土的聚羧酸外加剂。That is, the polycarboxylate admixture for machine-made sand concrete is obtained.
将乙二醇单乙烯基聚乙二醇醚(EPEG)单体为主要合成单元与丙烯酸及其衍生物在氧化还原引发体系作用下共聚合成一种梳型分子结构的抗泥型减水剂，其混凝土减水率≥32％；再通过与聚醚磷酸酯、有机控泡剂复合解决坍落度损失大和材料适应性差等问题，并且能明显增加混凝土强度；通过与混凝土粘度调节剂复配解决由于机制砂断级配、石粉波动和细沙含泥量波动引起的离析、泌水、扒底等现象。The ethylene glycol monovinyl polyglycol ether (EPEG) monomer is used as the main synthetic unit and acrylic acid and its derivatives are copolymerized under the action of a redox initiation system to form an anti-mud type water reducing agent with a comb-shaped molecular structure. Its concrete water reduction rate is ≥32%; then it can solve the problems of large slump loss and poor material adaptability by compounding with polyether phosphate and organic foam control agent, and can significantly increase the strength of concrete; it can be solved by compounding with concrete viscosity modifier Segregation, bleeding, bottom scraping and other phenomena caused by broken gradation of machine-made sand, fluctuation of stone powder and fluctuation of fine sand and mud content.
所述步骤(1)I中底料中乙二醇单乙烯基聚乙二醇醚的醚基与A料中丙烯酸的酸基摩尔数比为3～5：1。The molar ratio of the ether group of ethylene glycol monovinyl polyethylene glycol ether in the base material in the step (1) I to the acid group of the acrylic acid in the A material is 3 to 5:1.
所述步骤(1)I中底料和A料的溶质质量比为1：0.05～0.15。In the step (1) I, the solute mass ratio of the bottom material and the A material is 1:0.05-0.15.
所述步骤(1)I中底料中乙二醇单乙烯基聚乙二醇醚的分子量为2400、3000或6000。The molecular weight of ethylene glycol monovinyl polyglycol ether in the bottom material in described step (1) I is 2400, 3000 or 6000.
所述步骤(1)I中A料中链转移剂为巯基丙酸、巯基乙酸中的一种或两种的混合物。In the step (1) I, the chain transfer agent in material A is one or a mixture of mercaptopropionic acid and mercaptoacetic acid.
所述步骤(1)I中B料的还原剂是一种低温条件下可以和双氧水发生氧化还原反应的低温还原剂(H001)。The reductant of the B material in the step (1) I is a low-temperature reductant (H001) that can undergo an oxidation-reduction reaction with hydrogen peroxide under a low-temperature condition.
所述步骤(1)II中双氧水和B料的溶质质量比为0.8～2：1。In the step (1) II, the solute mass ratio of hydrogen peroxide and material B is 0.8-2:1.
所述步骤(1)II中底料单体EPEG与双氧水、B料的溶质质量和的比值为100：0.3～0.8。In the step (1) II, the ratio of the solute mass sum of the base material monomer EPEG to hydrogen peroxide and material B is 100:0.3-0.8.
所述步骤(1)制备的抗泥型聚羧酸减水剂，其混凝土减水率可达32％以上，且具备一定保坍性能。The mud-resistant polycarboxylate water-reducing agent prepared in the step (1) has a concrete water-reducing rate of more than 32%, and has a certain slump-preserving performance.
所述步骤(2)中的有机控泡剂为有机炔醇类物质，具有抑制混凝土大气泡的产生、引入微小气泡的作用，可直接替代传统的有机硅、聚醚类消泡剂和引气剂组合。The organic foam control agent in the step (2) is an organic alkynyl alcohol substance, which has the functions of inhibiting the generation of large bubbles in the concrete and introducing tiny bubbles, and can directly replace the traditional silicone, polyether defoamer and air-entraining agent. agent combination.
所述步骤(2)中的聚醚磷酸酯为一种对混凝土具有一定缓凝保坍作用且能增加抗压强度的作用的有机小分子物质。The polyether phosphate in the step (2) is an organic small molecular substance that has a certain effect of retarding setting and slump protection for concrete and can increase the compressive strength.
所述步骤(2)中的混凝土粘度调节剂为生物聚合外加剂，可以改变混凝土的流变特性，具有一定的保水作用，使混凝土在使用断级配机制砂且含石粉较多时不容易出现离析、泌水、扒底等现象。The concrete viscosity modifier in the step (2) is a biopolymeric admixture, which can change the rheological properties of the concrete and has a certain water retention effect, so that the concrete is not easily segregated when using broken graded machine-made sand and contains a lot of stone powder. , bleeding, scraping the bottom and other phenomena.
本发明中所合成的聚羧酸减水剂母液是以乙二醇单乙烯基聚乙二醇醚(EPEG)单体为主要原材料与丙烯酸或其衍生物在氧化还原反应体系引发作用下进行自由基共聚反应生成梳型分子结构的聚羧酸减水剂。其相对于传统的异丁烯醇聚氧乙烯醚(HPEG)、异戊烯醇聚氧乙烯醚(TPEG)合成的聚羧酸减水剂具有更大的旋转角，由于EPEG分子中的双键为一取代结构，进一步减少了聚醚侧链摆动的空间阻力，使得聚醚侧链的摆动更加自由，活动范围更大；聚醚侧链摆动自由度的增加，提高了聚醚侧链的包裹性和缠绕性，从而合成出的聚羧酸减水剂具有更优的适应性，尤其对于砂石料品质差、含泥量高的情况效果显著。The polycarboxylate water-reducing agent mother liquor synthesized in the present invention takes ethylene glycol monovinyl polyglycol ether (EPEG) monomer as the main raw material and acrylic acid or its derivatives under the action of redox reaction system. The polycarboxylate water-reducing agent with comb-shaped molecular structure is formed by the copolymerization of radicals. Compared with the polycarboxylate water reducing agent synthesized by traditional isobutenol polyoxyethylene ether (HPEG) and isopentenol polyoxyethylene ether (TPEG), it has a larger rotation angle, because the double bond in the EPEG molecule is one. The substitution structure further reduces the steric resistance of the swing of the polyether side chain, making the swing of the polyether side chain more free and the range of activities larger; the increase in the degree of freedom of the swing of the polyether side chain improves the encapsulation and flexibility of the polyether side chain. Therefore, the synthesized polycarboxylate water-reducing agent has better adaptability, especially in the case of poor sand and gravel quality and high mud content.
本发明中所选聚醚磷酸酯主要是一种含磷酸酯结构的有机分子化合物，对 机制砂中的石粉和细砂对聚羧酸减水剂的过度吸附具有明显的抑制作用，其作用主要是控制坍落度损失，对水泥具有一定的分散作用，并且能够有效地增加混凝土的中后期强度。The polyether phosphate selected in the present invention is mainly an organic molecular compound containing a phosphate structure, which has an obvious inhibitory effect on the excessive adsorption of the polycarboxylate water reducing agent by the stone powder and fine sand in the machine-made sand. It controls the slump loss, has a certain dispersing effect on the cement, and can effectively increase the strength of concrete in the middle and late stages.
本发明中有机炔醇类控泡剂能够控制混凝土中的气泡大小，消灭对混凝土有害作用的大气泡，留下对混凝土流动性和耐久性有改善作用的小气泡，替代了传统消泡剂和引气剂组分；并且与聚羧减水剂具有良好的相容性，不易因分层引起质量波动。The organic alkynyl alcohol foam control agent in the invention can control the size of air bubbles in concrete, eliminate large air bubbles that have harmful effects on concrete, and leave small air bubbles that can improve the fluidity and durability of concrete, replacing traditional defoamer and Air-entraining agent component; and has good compatibility with polycarboxylate water reducer, and is not easy to cause quality fluctuations due to delamination.
在机制砂中石粉含量和细砂中含泥量较高的情况下，常规以HPEG和TPEG单体为主要原材料合成的减水剂容易被过快吸附，坍落度损失较大，且拌制的混凝土和易性较差，离析、泌水现象较严重，单纯提高减水剂掺量已经不能明显改善混凝土的性能。因此本发明以EPEG为主体合成一种聚醚侧链空间活动阻力较小，自由度更大的聚羧酸减水剂，在应对断级配机制砂和含泥量高细沙方面有较好的作用。聚醚磷酸酯的的加入能够明显减小坍落度损失，并且能增加强度。有机控泡剂的引入可以明显调节混凝土的的气泡结构，消大泡，引入小气泡，改善混凝土的流动性。混凝土粘度调节材料的作用是提高混凝土的保水性，改善离析泌水现象。In the case of high stone powder content in machine-made sand and high mud content in fine sand, conventional water reducing agents synthesized with HPEG and TPEG monomers as the main raw materials are easily adsorbed too quickly, resulting in large slump loss and poor mixing. The workability of the concrete is poor, and the segregation and bleeding are more serious. Simply increasing the amount of water reducing agent can not significantly improve the performance of the concrete. Therefore, the present invention uses EPEG as the main body to synthesize a polycarboxylate water reducing agent with less resistance to the space movement of the polyether side chain and greater degree of freedom, which has better performance in dealing with broken-graded machine-made sand and fine sand with high mud content. effect. The addition of polyether phosphate can significantly reduce slump loss and increase strength. The introduction of organic foam control agent can significantly adjust the bubble structure of concrete, eliminate large bubbles, introduce small bubbles, and improve the fluidity of concrete. The function of concrete viscosity adjusting material is to improve the water retention of concrete and improve the phenomenon of segregation and bleeding.
本发明相比现有技术具有以下优点：Compared with the prior art, the present invention has the following advantages:
1、本发明制备的聚羧酸减水剂有效解决了机制砂石粉含量大和断级配引起的混凝土坍损大、和易性差以及强度不足等问题。1. The polycarboxylate water-reducing agent prepared by the present invention effectively solves the problems of large concrete slump, poor workability and insufficient strength caused by large content of machine-made sand and gravel powder and broken gradation.
2、本发明将抗泥型聚羧酸母液与聚醚磷酸酯、有机炔醇类控泡剂、粘度调节剂以及水复合的方法，明显改善了混凝土经时损失大、流动性差及和易性差的缺点。2. The method of compounding the anti-mud type polycarboxylic acid mother liquor with polyether phosphate, organic alkynyl alcohol foam control agent, viscosity regulator and water in the present invention significantly improves the concrete with large loss over time, poor fluidity and poor workability Shortcomings.
具体实施方式detailed description
下面对本发明的实施例作详细说明，实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。The embodiments of the present invention will be described in detail below. The embodiments are implemented on the premise of the technical solutions of the present invention, and detailed embodiments and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments. .
实施例1Example 1
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-3000)单体溶于200质量份水所得溶液作为底料，35质量份丙烯酸、1.8质量份巯基丙酸溶于15质量份水所得混合液作为A料，0.6质量份还原剂溶于40质量份水所得溶液作为B料；1. Preparation: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-3000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 35 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.6 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000002
Figure PCTCN2020120796-appb-000002
Figure PCTCN2020120796-appb-000003
Figure PCTCN2020120796-appb-000003
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为230/580*570mm、200/510*500mm、25.5MP、33.5MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*570mm, 200/510*500mm, 25.5MP, 33.5MP.
实施例2Example 2
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：240质量份乙二醇单乙烯基聚乙二醇醚(EPEG-2400)单体溶于200质量份水所得溶液作为底料，35质量份丙烯酸、1.8质量份巯基丙酸溶于15质量份水所得混合液作为A料，0.6质量份还原剂溶于40质量份水所得溶液作为B料；1. Preparation: 240 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-2400) monomers are dissolved in 200 parts by mass of water gained solution as primer, 35 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.6 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000004
Figure PCTCN2020120796-appb-000004
Figure PCTCN2020120796-appb-000005
Figure PCTCN2020120796-appb-000005
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为230/580*580mm、200/510*520mm、25.0MP、33.8MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*580mm, 200/510*520mm, 25.0MP, 33.8MP.
实施例3Example 3
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-6000)单体溶于200质量份水所得溶液作为底料，30质量份丙烯酸、1.5质量份巯基丙酸溶于15质量份水所得混合液作为A料，1.0质量份还原剂溶于40质量份水所得溶液作为B料；1. Preparation: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-6000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 30 parts by mass of acrylic acid, 1.5 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 1.0 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入4.0质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 4.0 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、 粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000006
Figure PCTCN2020120796-appb-000006
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为230/575*570mm、190/500*530mm、26.6MP、34.5MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/575*570mm, 190/500*530mm, 26.6MP, 34.5MP.
实施例4Example 4
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-3000)单体溶于200质量份水所得溶液作为底料，30质量份丙烯酸、1.8质量份巯基丙酸溶于15质量份水所得混合液作为A料，0.8质量份还原剂溶于40质量份水所得溶液作为B料；1. Prepare materials: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-3000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 30 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.8 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000007
Figure PCTCN2020120796-appb-000007
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为230/590*580mm、210/530*520mm、26.5MP、35.2MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/590*580mm, 210/530*520mm, 26.5MP, 35.2MP.
实施例5Example 5
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-3000)单体溶于200质量份水所得溶液作为底料，30质量份丙烯酸、1.8质量份巯基丙酸溶于15质量份水所得混合液作为A料，0.8质量份还原剂溶于40质量份水所得溶液作为B料；1. Prepare materials: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-3000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 30 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.8 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000008
Figure PCTCN2020120796-appb-000008
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为230/580*580mm、220/530*550mm、27.0MP、36.9MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*580mm, 220/530*550mm, 27.0MP, 36.9MP.
实施例6Example 6
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-3000)单体溶于200质量份水所得溶液作为底料，30质量份丙烯酸、1.8质量份巯基丙酸溶于15质量份水所得混合液作为A料，0.8质量份还原剂溶于40质量份水所得溶液作为B料；1. Prepare materials: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-3000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 30 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.8 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反 应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000009
Figure PCTCN2020120796-appb-000009
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为240/590*600mm、220/550*560mm、28.9MP、37.8MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 240/590*600mm, 220/550*560mm, 28.9MP, 37.8MP.
实施例7Example 7
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-3000)单体溶于200质量份水所得溶液作为底料，30质量份丙烯酸、1.8质量份巯基丙酸溶于15质量份水所得混合液作为A料，0.8质量份还原剂溶于40质量份水所得溶液作为B料；1. Prepare materials: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-3000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 30 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.8 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000010
Figure PCTCN2020120796-appb-000010
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为230/580*575mm、200/510*505mm、25.9MP、33.8MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*575mm, 200/510*505mm, 25.9MP, 33.8MP.
实施例8Example 8
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-3000)单体溶于200质量份水所得溶液作为底料，30质量份丙烯酸、1.8质量份巯基丙酸溶于15质 量份水所得混合液作为A料，0.8质量份还原剂溶于40质量份水所得溶液作为B料；1. Prepare materials: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-3000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 30 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.8 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000011
Figure PCTCN2020120796-appb-000011
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为230/580*580mm、200/510*510mm、26.3MP、34.7MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 230/580*580mm, 200/510*510mm, 26.3MP, 34.7MP.
实施例9Example 9
一种用于机制砂混凝土的聚羧酸外加剂制备方法，包括以下步骤，A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, comprising the following steps:
(1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
I.备料：300质量份乙二醇单乙烯基聚乙二醇醚(EPEG-3000)单体溶于200质量份水所得溶液作为底料，30质量份丙烯酸、1.8质量份巯基丙酸溶于15质量份水所得混合液作为A料，0.6质量份还原剂溶于40质量份水所得溶液作为B料；1. Prepare materials: 300 parts by mass of ethylene glycol monovinyl polyglycol ether (EPEG-3000) monomers are dissolved in 200 parts by mass of water obtained solution as primer, 30 parts by mass of acrylic acid, 1.8 parts by mass of mercaptopropionic acid are dissolved in The obtained mixed solution of 15 parts by mass of water is used as material A, and the solution obtained by dissolving 0.6 parts by mass of reducing agent in 40 parts by mass of water is used as material B;
II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入3.5质量份质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, then adding 3.5 parts by mass of hydrogen peroxide with a mass fraction of 27.5% to the reactor and stirring uniformly, then to the reaction Material A and material B were added dropwise to the kettle, and the dropwise addition was completed in 1.5 hours. After the dropwise addition, the reaction kettle was kept at 25-35 °C for 1 hour;
III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液，其混凝土减水率≥32％；III. Neutralization: adding lye to the product of step II and adjusting the pH at 5 to 7.5, and adding water until its solid content is 40% to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor, and its concrete water-reducing agent rate≥32%;
(2)复配(2) Compounding
将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下(10～35℃)按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor obtained in step (1) III is compounded in proportion with polyether phosphate, foam control agent, viscosity regulator, and water at normal temperature (10-35° C.), and each substance is The parts by mass are:
Figure PCTCN2020120796-appb-000012
Figure PCTCN2020120796-appb-000012
即得用于机制砂混凝土的聚羧酸外加剂，所得抗泥型聚羧酸外加剂混凝土初始坍落度/扩展度、1h坍落度/扩展度、7d抗压强度、28d抗压强度分别为240/590*610mm、220/550*570mm、29.3MP、38.4MP。That is, the polycarboxylate admixture for machine-made sand concrete is obtained, and the initial slump/expansion degree, 1h slump/expansion degree, 7d compressive strength and 28d compressive strength of the obtained mud-resistant polycarboxylate admixture concrete are respectively 240/590*610mm, 220/550*570mm, 29.3MP, 38.4MP.
由上述的实施例1-9制备所得的抗泥型聚羧酸外加剂混凝土具体性能如下表1.1。The specific properties of the mud-resistant polycarboxylic acid admixture concrete prepared by the above-mentioned Examples 1-9 are shown in Table 1.1 below.
表1.1 混凝土性能对比Table 1.1 Concrete performance comparison
Figure PCTCN2020120796-appb-000013
Figure PCTCN2020120796-appb-000013
通过以上实施例制备的用于机制砂混凝土的聚羧酸外加剂混凝土减水率高、抵抗坍落度损失能力强且混凝土和易性好，并且混凝土7d、28d抗压强度明显提高。The polycarboxylate admixture for machine-made sand concrete prepared by the above examples has high concrete water reduction rate, strong slump resistance resistance and good workability of concrete, and the compressive strength of concrete 7d and 28d is significantly improved.
上述的对实施例的描述是为便于该领域的普通技术人员能理解和发明。熟悉本领域的技术人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其它实施例中。本发明不限于以上实施例，本领域技术人员根据本发明的解释不脱离本发明的范畴所作出的改进和修改都在本专利的保护范围之内。The above description of the embodiments is for the convenience of understanding and invention by those of ordinary skill in the art. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles described herein may be applied to other embodiments. The present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art according to the explanation of the present invention without departing from the scope of the present invention are all within the protection scope of this patent.

Claims (9)

  1. 一种用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：包括以下步骤：A method for preparing a polycarboxylic acid admixture for machine-made sand concrete, characterized in that it comprises the following steps:
    (1)制备抗泥型聚羧酸减水剂母液(1) Preparation of mud-resistant polycarboxylate water-reducing agent mother liquor
    I.备料：乙二醇单乙烯基聚乙二醇醚单体溶于水所得溶液作为底料，丙烯酸、链转移剂溶于水所得混合液作为A料，还原剂溶于水所得溶液作为B料；1. material preparation: ethylene glycol monovinyl polyglycol ether monomer is dissolved in water gained solution as bottom material, acrylic acid, chain transfer agent are dissolved in water gained mixed solution as A material, reducing agent is dissolved in water gained solution as B material;
    II.氧化还原：将步骤I所得底料加入反应釜中，控制反应釜内温度在5～16℃，再向反应釜中加入质量分数为27.5％的双氧水后搅拌均匀，接着向反应釜中滴加A料和B料，1～1.5h滴加完成，滴加完后反应釜在25～35℃条件下保温1h；II. redox: adding the bottom material obtained in step 1 into the reactor, controlling the temperature in the reactor at 5～16 ℃, adding the hydrogen peroxide whose mass fraction is 27.5% in the reactor and stirring evenly, then dripping in the reactor Add material A and material B, and the dropwise addition is completed in 1-1.5 hours. After the dropwise addition, the reaction kettle is kept at 25-35 °C for 1 hour;
    III.中和：向步骤II生成物中加入碱液中和调节PH在5～7.5，再加水至其固含量为40％，即得抗泥型聚羧酸减水剂母液；III. Neutralization: adding lye in the product of step II and adjusting the pH at 5～7.5, and adding water to its solid content is 40%, to obtain the anti-mud type polycarboxylate water-reducing agent mother liquor;
    (2)复配(2) Compounding
    将步骤(1)III所得的抗泥型聚羧酸减水剂母液与聚醚磷酸酯、控泡剂、粘度调节剂、水在常温下按比例进行复配，各物质的质量份为：The anti-mud type polycarboxylate water-reducing agent mother liquor of step (1) III gained and polyether phosphate, foam control agent, viscosity modifier, water are compounded in proportion at normal temperature, and the mass parts of each material are:
    Figure PCTCN2020120796-appb-100001
    Figure PCTCN2020120796-appb-100001
    即得用于机制砂混凝土的聚羧酸外加剂。That is, the polycarboxylate admixture for machine-made sand concrete is obtained.
  2. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：所述步骤(1)I中底料中乙二醇单乙烯基聚乙二醇醚的醚基与A料中丙烯酸的酸基摩尔数比为3.5～5：1。The method for preparing a polycarboxylic acid admixture for machine-made sand concrete according to claim 1, characterized in that: the ether group of ethylene glycol monovinyl polyglycol ether in the bottom material in the step (1) I The molar ratio of acid groups to acrylic acid in material A is 3.5 to 5:1.
  3. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特 征在于：所述步骤(1)I中底料和A料的溶质质量比为1：0.05～0.15。The method for preparing a polycarboxylate admixture for machine-made sand concrete according to claim 1, wherein the solute mass ratio of the primer and the A material in the step (1) I is 1:0.05 to 0.15.
  4. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：所述步骤(1)I中底料中乙二醇单乙烯基聚乙二醇醚的分子量为2400、3000或6000。The method for preparing polycarboxylic acid admixture for machine-made sand concrete according to claim 1, is characterized in that: the molecular weight of ethylene glycol monovinyl polyglycol ether in the bottom material in described step (1) I is 2400, 3000 or 6000.
  5. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：所述步骤(1)I中A料中链转移剂为巯基丙酸、巯基乙酸中的一种或两种的混合物。The method for preparing a polycarboxylic acid admixture for machine-made sand concrete according to claim 1, wherein the chain transfer agent in the A material in the step (1) I is one of mercaptopropionic acid and mercaptoacetic acid. or a mixture of the two.
  6. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：所述步骤(1)II中双氧水和B料的溶质质量比为0.8～2：1。The method for preparing a polycarboxylic acid admixture for machine-made sand concrete according to claim 1, characterized in that: in the step (1) II, the solute mass ratio of hydrogen peroxide and material B is 0.8-2:1.
  7. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：所述步骤(1)II中底料乙二醇单乙烯基聚乙二醇醚单体质量与双氧水、B料的溶质质量和的比值为100：0.3～0.8。The method for preparing a polycarboxylic acid admixture for machine-made sand concrete according to claim 1, characterized in that: the quality of the primer ethylene glycol monovinyl polyglycol ether monomer in the step (1) II is equal to The ratio of solute mass sum of hydrogen peroxide and material B is 100:0.3～0.8.
  8. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：所述步骤(2)中的有机控泡剂为有机炔醇类物质。The method for preparing a polycarboxylic acid admixture for machine-made sand concrete according to claim 1, wherein the organic foam control agent in the step (2) is an organic alkynyl alcohol.
  9. 根据权利要求1所述的用于机制砂混凝土的聚羧酸外加剂制备方法，其特征在于：所述步骤(2)中的粘度调节剂为生物聚合外加剂。The method for preparing a polycarboxylic acid admixture for machine-made sand concrete according to claim 1, wherein the viscosity modifier in the step (2) is a biopolymeric admixture.
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CN116891371A (en) * 2023-09-11 2023-10-17 高密市东泰建材有限公司 Early-strength paving mortar and preparation method thereof
CN116891371B (en) * 2023-09-11 2023-11-24 高密市东泰建材有限公司 Early-strength paving mortar and preparation method thereof
CN117228983A (en) * 2023-09-27 2023-12-15 石家庄市长安育才建材有限公司 Additive for inhibiting flocculant in machine-made sand and preparation method thereof
CN117228983B (en) * 2023-09-27 2024-03-01 石家庄市长安育才建材有限公司 Additive for inhibiting flocculant in machine-made sand and preparation method thereof
CN117069415A (en) * 2023-10-16 2023-11-17 四川蜀道建筑科技有限公司 Anti-urinary polycarboxylate superplasticizer, concrete and preparation method thereof
CN117069415B (en) * 2023-10-16 2024-01-26 四川蜀道建筑科技有限公司 Anti-urinary polycarboxylate superplasticizer, concrete and preparation method thereof

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