WO2020133777A1 - Phosphate type polycarboxylate water reducer and preparation method - Google Patents

Phosphate type polycarboxylate water reducer and preparation method Download PDF

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Publication number
WO2020133777A1
WO2020133777A1 PCT/CN2019/080745 CN2019080745W WO2020133777A1 WO 2020133777 A1 WO2020133777 A1 WO 2020133777A1 CN 2019080745 W CN2019080745 W CN 2019080745W WO 2020133777 A1 WO2020133777 A1 WO 2020133777A1
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acid
phosphate
water
polymer
preparation
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PCT/CN2019/080745
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French (fr)
Chinese (zh)
Inventor
赖华珍
方云辉
赖广兴
邵幼哲
陈展华
郭元强
麻秀星
杨浩
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科之杰新材料集团有限公司
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Priority to MYPI2019002767A priority Critical patent/MY197298A/en
Publication of WO2020133777A1 publication Critical patent/WO2020133777A1/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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

Definitions

  • the invention relates to the technical field of building materials, in particular to a phosphate-type polycarboxylic acid water-reducing agent.
  • polycarboxylic acid water-reducing agent is mainly composed of polyether macromonomers and unsaturated carboxylic acid molecules through free radical polymerization. It has a strong adsorption tendency in clay minerals It has a very high sensitivity to aggregate mud content, which has a great impact on concrete transportation, working conditions and strength. Although national and industry standards have strict limits on the mud content and mud content indicators in concrete, due to the material conditions, the amount and type of sand used in concrete varies from place to place, resulting in polycarboxylic acid water reducers showing greater The difference between water reduction rate and slump retention, and it shows greater sensitivity to the change of the dosage.
  • the methods for dealing with high-mud content aggregates usually adopt two methods of over-mixing and compounding, where over-mixing will cause the concrete to initially segregate seriously, the gas content is high and seriously affects the appearance and later strength of the product;
  • Some additives such as sodium gluconate and citric acid are added to the water reducer. Although it can play a certain role in relief, it cannot fundamentally solve the problem of polycarboxylic acid water reducer in areas with high mud content. Adaptability issues.
  • the purpose of the present invention is to provide a phosphate-type polycarboxylic acid water-reducing agent and a preparation method thereof, aiming to solve the problem of poor adaptability of the polycarboxylic acid water-reducing agent to aggregates with high mud content in the prior art.
  • the present invention is achieved in this way, and provides a phosphate-type polycarboxylic acid water reducing agent, which is prepared by mixing the first polymer and the second polymer in a mass ratio of 1:1 to 5;
  • the first polymer is prepared by reacting raw materials with the following mass parts: 100-130 parts of polyacrylic acid, 300-350 parts of polyethylene glycol phosphate, antioxidants, and catalyst; wherein the amount of the catalyst is It is 0.1% to 1.0% of the total mass of the polyacrylic acid and the polyethylene glycol phosphate, and the amount of the antioxidant is 0.1% to the total mass of the polyacrylic acid and the polyethylene glycol phosphate. 1.0%;
  • the second polymer is prepared by reacting raw materials with the following mass parts: 300-500 parts of unsaturated polyether with molecular weight of 4000-6000, 5-18 parts of unsaturated phosphate ester, 12-40 parts of unsaturated acid, 30-50 parts of compound A and initiator and molecular weight regulator; wherein the dosage of the initiator is 0.1-3.0% of the total mass of the polyether monomer, and the dosage of the molecular weight regulator is 0.1 of the total mass of the polyether monomer ⁇ 2.0%, the structural formula of the compound A is:
  • R 1 is an alkyl group of 1 to 2 carbons
  • R 2 is H or CH 3
  • n is 20 to 100.
  • the invention provides a preparation method for preparing the above phosphate-type polycarboxylic acid water reducing agent, which includes the following steps:
  • the temperature is increased to 120 ⁇ 160°C, and the reduced-pressure esterification reaction is carried out;
  • the pressure was reduced to 80 mbar, and the heat preservation reaction was carried out for 3 to 6 hours. During the reaction, water was pumped out. After the reaction was completed, it was cooled to 60 to 80°C, diluted with distilled water, and the mass concentration of the polymer was adjusted to 45% to 55%;
  • the mass ratio of the polyacrylic acid to the polyethylene glycol phosphate is 100-130: 300-350, and the amount of the catalyst is 0.1%-1.0% of the total mass of the polyacrylic acid and polyethylene glycol phosphate.
  • the amount of the antioxidant is 0.1% to 1.0% of the total mass of polyacrylic acid and polyethylene glycol phosphate;
  • the obtained copolymer product is adjusted to pH 5-7 with alkali, and water is added to adjust the mass concentration of the copolymer product to 45-55%;
  • the mass ratio of the unsaturated polyether, the unsaturated phosphate ester, the unsaturated acid, and the compound A is 300-500: 5-18: 12-40: 30-50, and the amount of initiator used It is 0.1-3.0% of the total mass of the polyether monomer, and the amount of the molecular weight regulator is 0.1-2.0% of the total mass of the polyether monomer;
  • the structural formula of the compound A is:
  • R 1 is an alkyl group of 1 to 2 carbons, R 2 is H or CH 3 ; n is 20 to 100;
  • the first polymer and the second polymer are uniformly mixed in a mass ratio of 1:1 to 5 to obtain the phosphate-type polycarboxylic acid water-reducing agent.
  • the catalyst is at least one of ethylsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and 98% concentrated sulfuric acid.
  • the polyethylene glycol phosphate is polyethylene glycol (800) phosphate.
  • the unsaturated polyether with a molecular weight of 4000-6000 includes isobutylene alcohol polyoxyethylene ether and allyl polyoxyethylene ether, or includes isobutylene alcohol polyoxyethylene ether and isoamyl alcohol polyoxyethylene ether, or Including isobutylene alcohol polyoxyethylene ether.
  • the unsaturated acid is one of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride.
  • the unsaturated phosphate ester is hydroxybutyl methacrylate or hydroxybutyl phosphate acrylate.
  • the initiator is a water-soluble inorganic peroxy initiator or a water-soluble redox initiator system.
  • the water-soluble inorganic peroxy initiator is at least one of ammonium persulfate and potassium persulfate;
  • the water-soluble redox initiator system is hydrogen peroxide-Hangbai block, hydrogen peroxide-ascorbic acid and persulfate- At least one of sodium bisulfite.
  • the molecular weight regulator is at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium acetate and dodecanethiol.
  • the first polymer with an effective component molecular weight of 5000 to 20,000 is obtained by esterification of polyacrylic acid and polyethylene glycol phosphate, and the molecular weight of the effective component is obtained by copolymerization of unsaturated polyether, unsaturated phosphate ester, and compound A
  • the second polymer of 30,000 to 80,000 the first and second polymers are mixed in proportion, that is, the phosphate-type polycarboxylic acid water-reducing agent, because the molecular weight of the first polymer is small, it is preferentially adsorbed and intercalated into the clay
  • the adsorption of the second polymer by the clay is greatly reduced, thereby improving the adaptability of the water reducing agent to various gravel aggregates.
  • the phosphate-type polycarboxylic acid water-reducing agent described in the present invention contains phosphoric acid groups. Since the phosphate group has two negative charges, it has strong adsorption, so that the cement particles have a large amount of negative charge, and the same kind of charge is excluded. It will make the cement particles evenly dispersed; with time, the strong alkali environment of the concrete will cause the ester bond to hydrolyze, continuously releasing free phosphate, reacting with the cement hydration product, and forming dense and insoluble phosphate on the surface The thin layer prolongs the hydration induction period of cement, slows the hydration speed of C3A and plays a role of slump retention.
  • the present invention introduces a branch containing an imide group into the second polymer through a copolymerization reaction, which can further improve the dispersibility and dispersion retention of the water reducing agent.
  • This embodiment provides a method for preparing a phosphate-type polycarboxylic acid water-reducing agent, including:
  • Preparation of the first polymer 100.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C. Under nitrogen protection, 300.0g of polyethylene glycol phosphate and 1.12g are added Antioxidant (specifically Irganox 5057) and 2.30g catalyst (specifically ethylsulfonic acid), then, the temperature was increased to 155 ⁇ 160 °C, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction 4h, during The water is removed by vacuuming. After the reaction is completed, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
  • Antioxidant specifically Irganox 5057
  • 2.30g catalyst specifically ethylsulfonic acid
  • R 1 is -CH 2 CH 2
  • R 2 is H
  • n 40.
  • the structural formulas of Compound A are all shown in the structural formulas, and the description will not be repeated.
  • Preparation of the first polymer 130.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C, and under the protection of nitrogen, 350.0g of polyethylene glycol phosphate and 2.40g are added Irganox 5057 antioxidant and 3.67g benzenesulfonic acid, then, the temperature was increased to 150 ⁇ 155 °C, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction for 5h, during which water was removed by vacuum, the reaction was completed After that, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
  • Preparation of the first polymer 115.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C, and under the protection of nitrogen, 342.0g of polyethylene glycol phosphate and 2.67g are added Irganox 5057 antioxidant and 4.88g p-toluenesulfonic acid, then, the temperature was raised to 155 ⁇ 160 °C, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction for 3h, during which water was removed by vacuum method, the reaction After the end, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
  • the first polymer prepared in step (1) and the second polymer prepared in step (2) are uniformly mixed in a mass ratio of 1:1 to obtain the phosphate-type polycarboxylic acid water-reducing agent.
  • Preparation of the first polymer 110.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C. Under the protection of nitrogen, 336.0g of polyethylene glycol phosphate and 2.51g are added Irganox 5057 antioxidant and 5.60g 98% concentrated sulfuric acid, then, the temperature was raised to 155 ⁇ 160 °C, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction 6h, during which water was removed by vacuum method, the reaction After the end, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
  • the first polymer prepared in step (1) and the second polymer prepared in step (2) are uniformly mixed in a mass ratio of 1:3.5 to obtain the phosphate-type polycarboxylic acid water reducing agent.
  • the polycarboxylic acid water-reducing agents prepared in Examples 1 to 4 were tested, and when the amount of solid content is 0.12% (relative to the amount of benchmark cement), the water-reducing rate is higher than 40 %, 3d compressive strength ratio is greater than 170%, 7d compressive strength ratio is greater than 150%, 28d compressive strength ratio is greater than 145%, 28d shrinkage ratio is less than 105%.
  • the benchmark and Minfu PO 42.5 ordinary Portland cement are adopted respectively, and the concrete mix ratio is: cement 300kg/m 3 , fly ash 100kg/m 3 , mineral powder 100kg/m 3 , sand 690kg/m 3 , stone 1050kg/m 3. Water 160kg/m 3 , and add 3.5% bentonite (relative to the amount of cement), the phosphate-type polycarboxylic acid water-reducing agent prepared in Examples 1 to 4 and the commercially available polycarboxylic acid water-reducing agent (PCE) Performance test, by adjusting the amount of water reducing agent, so that the initial expansion of concrete is equivalent.
  • PCE polycarboxylic acid water-reducing agent
  • the phosphate-type polycarboxylic acid water-reducing agent synthesized in the present invention has a greater water reduction rate than the commercially available polycarboxylic acid water-reducing agent (PCE).
  • PCE polycarboxylic acid water-reducing agent
  • the slump retention performance is better, so it can be seen that the polycarboxylic acid water reducing agent prepared by the invention has relatively low sensitivity to materials with high mud content and has an anti-mud effect, and at the same time, the phosphate type polycarboxylic acid water reducing agent provided by the invention It shows good dispersibility and dispersion retention in different cements, better adaptability and better overall performance.

Abstract

A phosphate type polycarboxylate water reducer and a preparation method. A first polymer of which the molecular weight of an effective component is 5,000-20,000 is obtained by means of esterification between polyacrylic acid and polyethylene glycol phosphate; a second polymer of which the molecular weight of an effective component is 30,000-80,000 is obtained by means of copolymerization of an unsaturated polyether, an unsaturated phosphate, and compound A; the phosphate type polycarboxylate water reducer is obtained by mixing the first and second polymers in proportion. The first polymer has the smaller molecular weight, and thus is preferentially adsorbed and intercalated in a layered structure of clay, thereby reducing adsorption of the clay on the second polymer and thus enhancing adaptability of the water reducer on various gravel aggregates.

Description

一种磷酸盐型聚羧酸减水剂和制备方法Phosphate type polycarboxylic acid water reducing agent and preparation method 技术领域Technical field
本发明涉及建筑材料的技术领域，尤其涉及一种磷酸盐型聚羧酸减水剂。The invention relates to the technical field of building materials, in particular to a phosphate-type polycarboxylic acid water-reducing agent.
背景技术Background technique
随着国家大规模基础设施的建设，聚羧酸减水剂也越来越广泛地被应用在混凝土工程中。而现代混凝土的原材料状况却日趋严峻，工业副产石膏作为水泥调凝剂的使用导致胶凝材料SO4 2-含量偏高；粉煤灰、矿渣粉、煤矸石等大宗工业固体废弃物的广泛应用，使得胶凝材料的组份更加复杂；特别是优质砂、石资源日益匮乏，骨料含泥量和吸水率增大，直接影响混凝土外加剂与材料之间的适应性，导致混凝土初始流动度和流动度保持能力大幅降低，极大限制了高效减水剂的推广应用。 With the construction of large-scale national infrastructure, polycarboxylic acid water-reducing agent is also more and more widely used in concrete engineering. However, the raw materials of modern concrete are becoming more and more serious. The use of industrial by-product gypsum as a cement setting agent leads to a high content of cementing material SO4 2- ; fly ash, slag powder, coal gangue and other large industrial solid wastes are widely used , Which makes the composition of cementing materials more complicated; especially the high quality sand and stone resources are increasingly scarce, and the aggregate mud content and water absorption rate increase, which directly affects the adaptability between concrete admixtures and materials, resulting in the initial fluidity of concrete And the ability to maintain fluidity is greatly reduced, which greatly limits the promotion and application of high-efficiency water-reducing agents.
聚羧酸减水剂作为一种高性能减水剂，其分子结构主要由聚醚大单体和不饱和的羧酸分子经自由基聚合而成，其在黏土矿物中具有较强的吸附趋势，对骨料含泥量有极高的敏感度，这对混凝土运输、工作状态以及强度都带来很大的影响。虽然国家及行业标准对混凝土中含泥量、泥块含量指标有严格限制，然而受材料条件限制，各地混凝土用砂量以及种类不同，造成聚羧酸减水剂在这些地方表现出较大的减水率和保坍性差异性，且对掺量的变化体现出较大的敏感性。As a high-performance water-reducing agent, polycarboxylic acid water-reducing agent is mainly composed of polyether macromonomers and unsaturated carboxylic acid molecules through free radical polymerization. It has a strong adsorption tendency in clay minerals It has a very high sensitivity to aggregate mud content, which has a great impact on concrete transportation, working conditions and strength. Although national and industry standards have strict limits on the mud content and mud content indicators in concrete, due to the material conditions, the amount and type of sand used in concrete varies from place to place, resulting in polycarboxylic acid water reducers showing greater The difference between water reduction rate and slump retention, and it shows greater sensitivity to the change of the dosage.
目前应对高含泥量骨料的方法，通常采用超掺量和复配两种方法，其中超掺会使混凝土初始严重离析，含气量高且严重影响制品外观和后期强度；而在聚羧酸减水剂中复配一些助剂如缓凝剂葡萄糖酸钠、柠檬酸等，虽然能起到一定的缓解作用，但并不能从根本上解决聚羧酸减水剂在高含泥量地区的适应性问题。At present, the methods for dealing with high-mud content aggregates usually adopt two methods of over-mixing and compounding, where over-mixing will cause the concrete to initially segregate seriously, the gas content is high and seriously affects the appearance and later strength of the product; Some additives such as sodium gluconate and citric acid are added to the water reducer. Although it can play a certain role in relief, it cannot fundamentally solve the problem of polycarboxylic acid water reducer in areas with high mud content. Adaptability issues.
因此，设计合成具有新颖结构的聚羧酸减水剂以解决实际工程应用需要成为本领域技术人员急待解决的技术难关。Therefore, designing and synthesizing a polycarboxylic acid water-reducing agent with a novel structure to solve practical engineering application needs has become a technical difficulty that those skilled in the art urgently need to solve.
发明内容Summary of the invention
本发明的目的在于提供一种磷酸盐型聚羧酸减水剂和制备方法，旨在解决现有技术中聚羧酸减水剂对于高含泥量骨料的适应性较差的问题。The purpose of the present invention is to provide a phosphate-type polycarboxylic acid water-reducing agent and a preparation method thereof, aiming to solve the problem of poor adaptability of the polycarboxylic acid water-reducing agent to aggregates with high mud content in the prior art.
本发明是这样实现的，提供了一种磷酸盐型聚羧酸减水剂，由第一聚合物和第二聚合物按质量比1:1～5混合制得；The present invention is achieved in this way, and provides a phosphate-type polycarboxylic acid water reducing agent, which is prepared by mixing the first polymer and the second polymer in a mass ratio of 1:1 to 5;
其中，所述第一聚合物按照由以下质量份数的原料反应制得：聚丙烯酸100～130份、聚乙二醇磷酸酯300～350份以及抗氧剂、催化剂；其中所述催化剂的用量为所述聚丙烯酸与所述聚乙二醇磷酸酯总质量的0.1％～1.0％，所述抗氧剂的用量为所述聚丙烯酸与所述聚乙二醇磷酸酯总质量的0.1％～1.0％；Wherein, the first polymer is prepared by reacting raw materials with the following mass parts: 100-130 parts of polyacrylic acid, 300-350 parts of polyethylene glycol phosphate, antioxidants, and catalyst; wherein the amount of the catalyst is It is 0.1% to 1.0% of the total mass of the polyacrylic acid and the polyethylene glycol phosphate, and the amount of the antioxidant is 0.1% to the total mass of the polyacrylic acid and the polyethylene glycol phosphate. 1.0%;
所述第二聚合物按照由以下质量份数的原料反应制得：分子量为4000～6000的不饱和聚醚300～500份、不饱和磷酸酯5～18份、不饱和酸12～40份、化合物A 30～50份以及引发剂、分子量调节剂；其中所述引发剂的用量为聚醚单体总质量的0.1～3.0％，所述分子量调节剂的用量为聚醚单体总质量的0.1～2.0％，所述化合物A的结构式为：The second polymer is prepared by reacting raw materials with the following mass parts: 300-500 parts of unsaturated polyether with molecular weight of 4000-6000, 5-18 parts of unsaturated phosphate ester, 12-40 parts of unsaturated acid, 30-50 parts of compound A and initiator and molecular weight regulator; wherein the dosage of the initiator is 0.1-3.0% of the total mass of the polyether monomer, and the dosage of the molecular weight regulator is 0.1 of the total mass of the polyether monomer ~2.0%, the structural formula of the compound A is:
Figure PCTCN2019080745-appb-000001
Figure PCTCN2019080745-appb-000001
其中，R 1为1～2个碳的烷基，R 2为H或CH 3，；n为20～100。 Wherein R 1 is an alkyl group of 1 to 2 carbons, R 2 is H or CH 3 , and n is 20 to 100.
本发明提供用于制备上述磷酸盐型聚羧酸减水剂的制备方法，包括如下步骤：The invention provides a preparation method for preparing the above phosphate-type polycarboxylic acid water reducing agent, which includes the following steps:
(1)制备第一聚合物：将质量分数为55％的聚丙烯酸加入反应容器中加热到50～70℃，在氮气保护下，再加入聚乙二醇磷酸酯、抗氧剂和催化剂；(1) Preparation of the first polymer: Polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C, and under the protection of nitrogen, polyethylene glycol phosphate, antioxidant and catalyst are added;
温度升高到120～160℃，进行减压酯化反应；The temperature is increased to 120～160℃, and the reduced-pressure esterification reaction is carried out;
压力降到80mbar，保温反应3～6h，期间抽除去水，反应结束后冷却至60～80℃，加入蒸馏水稀释，调节聚合物的质量浓度至45～55％；The pressure was reduced to 80 mbar, and the heat preservation reaction was carried out for 3 to 6 hours. During the reaction, water was pumped out. After the reaction was completed, it was cooled to 60 to 80°C, diluted with distilled water, and the mass concentration of the polymer was adjusted to 45% to 55%;
其中，所述聚丙烯酸与所述聚乙二醇磷酸酯质量比为100～130：300～350，所述催化剂的用量为聚丙烯酸与聚乙二醇磷酸酯总质量的0.1％～1.0％，所述抗氧剂的用量为聚丙烯酸与聚乙二醇磷酸酯总质量的0.1％～1.0％；Wherein, the mass ratio of the polyacrylic acid to the polyethylene glycol phosphate is 100-130: 300-350, and the amount of the catalyst is 0.1%-1.0% of the total mass of the polyacrylic acid and polyethylene glycol phosphate. The amount of the antioxidant is 0.1% to 1.0% of the total mass of polyacrylic acid and polyethylene glycol phosphate;
(2)制备第二聚合物：将分子量为4000～6000的不饱和聚醚、不饱和磷酸酯、不饱和酸、化合物A与去离子水加入反应容器中混合，将引发剂水溶液与分子量调节剂溶液滴入反应容器步进行反应，反应温度为10～60℃，滴加时间为2.0～8.0h，滴加完毕后保温0～2.0h；(2) Preparation of the second polymer: Add unsaturated polyether with molecular weight of 4000-6000, unsaturated phosphate ester, unsaturated acid, compound A and deionized water to the reaction vessel and mix them, and mix the initiator aqueous solution and molecular weight regulator The solution is dropped into the reaction vessel to carry out the reaction, the reaction temperature is 10 to 60 ℃, the dropping time is 2.0 to 8.0h, and the temperature is kept for 0 to 2.0h after the dropping is completed;
制得共聚产物用碱调节pH至5～7，补加水调节共聚产物的质量浓度为45～55％；The obtained copolymer product is adjusted to pH 5-7 with alkali, and water is added to adjust the mass concentration of the copolymer product to 45-55%;
其中，所述不饱和聚醚、所述不饱和磷酸酯、所述不饱和酸、所述化合物A的质量比为300～500：5～18：12～40：30～50，引发剂的用量为聚醚单体总质量的0.1～3.0％，分子量调节剂的用量为聚醚单体总质量的0.1～2.0％；所述化合物A的结构式为：Wherein, the mass ratio of the unsaturated polyether, the unsaturated phosphate ester, the unsaturated acid, and the compound A is 300-500: 5-18: 12-40: 30-50, and the amount of initiator used It is 0.1-3.0% of the total mass of the polyether monomer, and the amount of the molecular weight regulator is 0.1-2.0% of the total mass of the polyether monomer; the structural formula of the compound A is:
Figure PCTCN2019080745-appb-000002
Figure PCTCN2019080745-appb-000002
其中，R 1为1～2个碳的烷基，R 2为H或CH 3，；n为20～100； Among them, R 1 is an alkyl group of 1 to 2 carbons, R 2 is H or CH 3 ; n is 20 to 100;
(3)将所述第一聚合物和所述第二聚合物按1:1～5的质量比混合均匀，获得所述磷酸盐型聚羧酸减水剂。(3) The first polymer and the second polymer are uniformly mixed in a mass ratio of 1:1 to 5 to obtain the phosphate-type polycarboxylic acid water-reducing agent.
优选的，所述催化剂为乙基磺酸、苯磺酸、对甲苯磺酸和98％的浓硫酸中的至少一种。Preferably, the catalyst is at least one of ethylsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and 98% concentrated sulfuric acid.
优选的，所述聚乙二醇磷酸酯为聚乙二醇(800)磷酸酯。Preferably, the polyethylene glycol phosphate is polyethylene glycol (800) phosphate.
优选的，所述分子量为4000～6000的不饱和聚醚包括异丁烯醇聚氧乙烯醚和烯丙基聚氧乙烯醚，或者包括异丁烯醇聚氧乙烯醚和异戊烯醇聚氧乙烯醚，或者包括异丁烯醇聚氧乙烯醚。Preferably, the unsaturated polyether with a molecular weight of 4000-6000 includes isobutylene alcohol polyoxyethylene ether and allyl polyoxyethylene ether, or includes isobutylene alcohol polyoxyethylene ether and isoamyl alcohol polyoxyethylene ether, or Including isobutylene alcohol polyoxyethylene ether.
优选的，所述不饱和酸为丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸、衣康酸酐中的一种。Preferably, the unsaturated acid is one of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride.
优选的，所述不饱和磷酸酯为甲基丙烯酸羟丁基磷酸酯或丙烯酸羟丁基磷酸酯。Preferably, the unsaturated phosphate ester is hydroxybutyl methacrylate or hydroxybutyl phosphate acrylate.
优选的，所述引发剂为水溶性无机过氧类引发剂或水溶性氧化还原引发体系。Preferably, the initiator is a water-soluble inorganic peroxy initiator or a water-soluble redox initiator system.
优选的，所述水溶性无机过氧类引发剂为过硫酸铵、过硫酸钾中的至少一种；所述水溶性氧化还原引发体系为双氧水-吊白块、双氧水-抗坏血酸和过硫酸盐-亚硫酸氢钠中的至少一种。Preferably, the water-soluble inorganic peroxy initiator is at least one of ammonium persulfate and potassium persulfate; the water-soluble redox initiator system is hydrogen peroxide-Hangbai block, hydrogen peroxide-ascorbic acid and persulfate- At least one of sodium bisulfite.
优选的，所述分子量调节剂为巯基乙酸、巯基丙酸、巯基乙醇、异丙醇、乙酸钠和十二硫醇中的至少一种。Preferably, the molecular weight regulator is at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium acetate and dodecanethiol.
本发明的有益效果是：The beneficial effects of the invention are:
1、本发明通过聚丙烯酸与聚乙二醇磷酸酯酯化得到有效成分的分子量为5000～20000的第一聚合物，通过不饱聚醚，不饱和磷酸酯，化合物A共聚得到有效成分分子量为30000～80000的第二聚合物，将第一、第二聚合物按比例混合即所述磷酸盐型聚羧酸减水剂，由于第一聚合物分子量较小，优先被吸附插层到粘土的层状结构中，大大降低粘土对第二聚合物的吸附，从而提高减水剂对各种砂石骨料的适应性。1. In the present invention, the first polymer with an effective component molecular weight of 5000 to 20,000 is obtained by esterification of polyacrylic acid and polyethylene glycol phosphate, and the molecular weight of the effective component is obtained by copolymerization of unsaturated polyether, unsaturated phosphate ester, and compound A For the second polymer of 30,000 to 80,000, the first and second polymers are mixed in proportion, that is, the phosphate-type polycarboxylic acid water-reducing agent, because the molecular weight of the first polymer is small, it is preferentially adsorbed and intercalated into the clay In the layered structure, the adsorption of the second polymer by the clay is greatly reduced, thereby improving the adaptability of the water reducing agent to various gravel aggregates.
2、本发明所述磷酸盐型聚羧酸减水剂含有磷酸基，由于磷酸根带有两个负电荷，具有强烈的吸附性，使水泥颗粒带有大量的负电荷，同种电荷的排斥力使水泥颗粒均匀分散；随着时间的推移，混凝土强碱的环境会使酯键发生水解，持续释放出游离的磷酸根，与水泥水化产物发生反应，在表面形成致密难溶的磷酸根薄层，延长水泥水化诱导期，使C3A水化速度减缓而起到保坍的作用。2. The phosphate-type polycarboxylic acid water-reducing agent described in the present invention contains phosphoric acid groups. Since the phosphate group has two negative charges, it has strong adsorption, so that the cement particles have a large amount of negative charge, and the same kind of charge is excluded. It will make the cement particles evenly dispersed; with time, the strong alkali environment of the concrete will cause the ester bond to hydrolyze, continuously releasing free phosphate, reacting with the cement hydration product, and forming dense and insoluble phosphate on the surface The thin layer prolongs the hydration induction period of cement, slows the hydration speed of C3A and plays a role of slump retention.
3、本发明通过共聚反应在第二聚合物中引入了含有酰亚胺基的支链，可进一步提高减水剂的分散性和分散保持性。3. The present invention introduces a branch containing an imide group into the second polymer through a copolymerization reaction, which can further improve the dispersibility and dispersion retention of the water reducing agent.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the following describes the present invention in further detail with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not intended to limit the present invention.
实施例1Example 1
本实施例中提供一种磷酸盐型聚羧酸减水剂的制备方法，包括：This embodiment provides a method for preparing a phosphate-type polycarboxylic acid water-reducing agent, including:
(1)第一聚合物的制备：将100.0g质量分数为55％的聚丙烯酸加入反应容器中加热到50～70℃，在氮气保护下，再加入300.0g聚乙二醇磷酸酯、1.12g抗氧剂(具体为Irganox 5057)和2.30g催化剂(具体为乙基磺酸)，随后，温度升高到155～160℃，进行减压酯化反应，压力降到80mbar，保温反应4h，期间用抽真空的方法除去水，反应结束后将产品冷却至60～80℃，加入蒸馏水稀释，调节聚合物的质量浓度为45～55％。(1) Preparation of the first polymer: 100.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C. Under nitrogen protection, 300.0g of polyethylene glycol phosphate and 1.12g are added Antioxidant (specifically Irganox 5057) and 2.30g catalyst (specifically ethylsulfonic acid), then, the temperature was increased to 155 ~ 160 ℃, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction 4h, during The water is removed by vacuuming. After the reaction is completed, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
(2)第二聚合物的制备：将340.0g分子量为4000的异丁烯醇聚氧乙烯醚、10.0g甲基丙烯酸羟丁基磷酸酯、21.0g丙烯酸、35.0g化合物A与200.0g去离子水加入反应容器中混合，将过硫酸铵水溶液(其中过硫酸铵3.10g，水30.00g)、巯基乙醇水溶液(其中巯基乙醇2.42g，水30.00g)滴入反应容器中进行反应，反应温度为60℃，滴加时间为6.0h，滴加完毕后保温2h，制得的共聚产物用碱调节pH至5～7，补加水调节聚合物的质量浓度为45～55％。其中，化合物A的结构式为
Figure PCTCN2019080745-appb-000003
(2) Preparation of the second polymer: 340.0 g of polyoxyethylene isobutenol with a molecular weight of 4000, 10.0 g of hydroxybutyl methacrylate phosphate, 21.0 g of acrylic acid, 35.0 g of compound A and 200.0 g of deionized water are added Mix in the reaction vessel, and drop an ammonium persulfate aqueous solution (ammonium persulfate 3.10g, water 30.00g) and mercaptoethanol aqueous solution (among them, mercaptoethanol 2.42g, water 30.00g) into the reaction vessel for reaction. The reaction temperature is 60℃ The dripping time is 6.0h. After the dripping is completed, heat is maintained for 2h. The prepared copolymer product is adjusted to pH 5-7 with alkali, and water is added to adjust the mass concentration of the polymer to 45-55%. Among them, the structural formula of compound A is
Figure PCTCN2019080745-appb-000003
R 1为-CH 2CH 2，R 2为H，n为40。下文中，化合物A的结构式均为该结构式所示，不再重复叙述。 R 1 is -CH 2 CH 2 , R 2 is H, and n is 40. Hereinafter, the structural formulas of Compound A are all shown in the structural formulas, and the description will not be repeated.
(3)将步骤(1)制得的第一聚合物和步骤(2)制得的第二聚合物按质量比1：3混合均匀，即得所述磷酸盐型聚羧酸减水剂。(3) Mix the first polymer prepared in step (1) and the second polymer prepared in step (2) in a mass ratio of 1:3 to obtain the phosphate-type polycarboxylic acid water reducing agent.
实施例2Example 2
(1)第一聚合物的制备：将130.0g质量分数为55％的聚丙烯酸加入反应容器中加热到50～70℃，在氮气保护下，再加入350.0g聚乙二醇磷酸酯、2.40g Irganox 5057抗氧剂和3.67g苯磺酸，随后，温度升高到150～155℃，进行减压酯化反应，压力降到80mbar，保温反应5h，期间用抽真空的方法除去水，反应结束后将产品冷却至60～80℃，加入蒸馏水稀释，调节聚合物的质量浓度为45～55％。(1) Preparation of the first polymer: 130.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C, and under the protection of nitrogen, 350.0g of polyethylene glycol phosphate and 2.40g are added Irganox 5057 antioxidant and 3.67g benzenesulfonic acid, then, the temperature was increased to 150 ~ 155 ℃, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction for 5h, during which water was removed by vacuum, the reaction was completed After that, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
(2)第二聚合物的制备：将40.0g分子量为4000的甲基烯丙醇聚氧乙烯醚和360.0g 分子量为6000的异丁烯醇聚氧乙烯醚、5.0g甲基丙烯酸羟丁基磷酸酯、40.0g马来酸酐、50.0g化合物A(R 1为-CH 2CH 2，R 2为CH 3，n为50)与200.0g去离子水加入反应容器中混合，将双氧水水溶液(其中双氧水3.20g，水30.00g)、吊白块水溶液(其中吊白块2.60g，水30.00g)、巯基丙酸水溶液(其中巯基丙酸3.0g，水30.00g)滴入反应容器中进行反应，反应温度为40℃，滴加时间为6h，滴加完毕后保温1h，制得的共聚产物用碱调节pH至5～7，补加水调节聚合物的质量浓度为45～55％。 (2) Preparation of the second polymer: 40.0 g of methallyl alcohol polyoxyethylene ether with a molecular weight of 4000, 360.0 g of a methacrylate polyoxyethylene ether with a molecular weight of 6000, and 5.0 g of hydroxybutyl methacrylate phosphate , 40.0 g of maleic anhydride, 50.0 g of compound A (R 1 is -CH 2 CH 2 , R 2 is CH 3 , n is 50) and 200.0 g of deionized water are added to the reaction vessel and mixed, and hydrogen peroxide aqueous solution (including hydrogen peroxide 3.20 g, water 30.00g), hanging white block aqueous solution (including hanging white block 2.60g, water 30.00g), mercaptopropionic acid aqueous solution (including mercaptopropionic acid 3.0g, water 30.00g) was dropped into the reaction vessel for reaction, reaction temperature The temperature is 40℃, the dropping time is 6 hours, and the temperature is kept for 1 hour after the dropping is completed. The prepared copolymer product is adjusted to pH 5-7 with alkali, and water is added to adjust the mass concentration of the polymer to 45-55%.
(3)将步骤(1)制得的第一聚合物和步骤(2)制得的第二聚合物按质量比1：5混合均匀，即得所述磷酸盐型聚羧酸减水剂。(3) Mix the first polymer prepared in step (1) and the second polymer prepared in step (2) in a mass ratio of 1:5 to obtain the phosphate-type polycarboxylic acid water-reducing agent.
实施例3Example 3
(1)第一聚合物的制备：将115.0g质量分数为55％的聚丙烯酸加入反应容器中加热到50～70℃，在氮气保护下，再加入342.0g聚乙二醇磷酸酯、2.67g Irganox 5057抗氧剂和4.88g对甲苯磺酸，随后，温度升高到155～160℃，进行减压酯化反应，压力降到80mbar，保温反应3h，期间用抽真空的方法除去水，反应结束后将产品冷却至60～80℃，加入蒸馏水稀释，调节聚合物的质量浓度为45～55％。(1) Preparation of the first polymer: 115.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C, and under the protection of nitrogen, 342.0g of polyethylene glycol phosphate and 2.67g are added Irganox 5057 antioxidant and 4.88g p-toluenesulfonic acid, then, the temperature was raised to 155 ~ 160 ℃, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction for 3h, during which water was removed by vacuum method, the reaction After the end, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
(2)第二聚合物的制备：将100.0g分子量为6000的异戊烯醇聚氧乙烯醚和300.0g分子量为6000的异丁烯醇聚氧乙烯醚、18.0g丙烯酸羟丁基磷酸酯、12.0g衣康酸、30.0g化合物A(R1为-CH 2，R 2为CH 3，n为40)与200.0g去离子水加入反应容器中混合，过硫酸铵水溶液(其中过硫酸铵5.00g，水30.00g)、亚硫酸氢钠水溶液(其中亚硫酸氢钠4.00g，水30.00g)、异丙醇水溶液(其中异丙醇3.30g，水30.00g)滴入反应容器中进行反应，反应温度为50℃，滴加时间为8h，滴加完毕后保温0h，制得的共聚产物用碱调节pH至5～7，补加水调节聚合物的质量浓度为45～55％。 (2) Preparation of the second polymer: 100.0 g of prenyl alcohol polyoxyethylene ether with a molecular weight of 6000 and 300.0 g of a polyoxyethylene isobutylene alcohol with a molecular weight of 6000, 18.0 g of hydroxybutyl phosphate acrylate, 12.0 g Itaconic acid, 30.0 g of compound A (R1 is -CH 2 , R 2 is CH 3 , n is 40) and 200.0 g of deionized water are added to the reaction vessel, and an aqueous solution of ammonium persulfate (ammonium persulfate 5.00 g, water 30.00g), an aqueous solution of sodium bisulfite (including 4.00g of sodium bisulfite and 30.00g of water), and an aqueous solution of isopropyl alcohol (of which 3.30g of isopropyl alcohol and 30.00g of water) are dropped into the reaction vessel for reaction, and the reaction temperature is At 50°C, the dropping time was 8 hours, and the temperature was kept at 0 hours after the dropping was completed. The prepared copolymer product was adjusted to pH 5-7 with alkali, and water was added to adjust the mass concentration of the polymer to 45-55%.
(3)将步骤(1)制得的第一聚合物和步骤(2)制得的第二聚合物按质量比1：1混合均匀，即得所述磷酸盐型聚羧酸减水剂。(3) The first polymer prepared in step (1) and the second polymer prepared in step (2) are uniformly mixed in a mass ratio of 1:1 to obtain the phosphate-type polycarboxylic acid water-reducing agent.
实施例4Example 4
(1)第一聚合物的制备：将110.0g质量分数为55％的聚丙烯酸加入反应容器中加热到50～70℃，在氮气保护下，再加入336.0g聚乙二醇磷酸酯、2.51g Irganox 5057抗氧剂和 5.60g98％的浓硫酸，随后，温度升高到155～160℃，进行减压酯化反应，压力降到80mbar，保温反应6h，期间用抽真空的方法除去水，反应结束后将产品冷却至60～80℃，加入蒸馏水稀释，调节聚合物的质量浓度为45～55％。(1) Preparation of the first polymer: 110.0g of polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C. Under the protection of nitrogen, 336.0g of polyethylene glycol phosphate and 2.51g are added Irganox 5057 antioxidant and 5.60g 98% concentrated sulfuric acid, then, the temperature was raised to 155 ~ 160 ℃, under reduced pressure esterification reaction, the pressure was reduced to 80mbar, holding reaction 6h, during which water was removed by vacuum method, the reaction After the end, the product is cooled to 60-80°C, diluted with distilled water, and the mass concentration of the polymer is adjusted to 45-55%.
(2)第二聚合物的制备：将220.0g分子量为5000的异戊烯醇聚氧乙烯醚和240g分子量为4000的异丁烯醇聚氧乙烯醚、10.0g丙烯酸羟丁基磷酸酯、25.0g马来酸、40.0g化合物A(R 1为-CH 2，R 2为H，n为100)与200.0g去离子水加入反应容器中混合，双氧水水溶液(其中双氧水3.20g，水30.00g)、抗坏血酸水溶液(其中抗坏血酸1.00g，水30.00g)、巯基丙酸水溶液(其中巯基丙酸2.75g，水30.00g)反应温度为常温，滴加时间为6.0h，滴加完毕后保温1h，制得的共聚产物用碱调节pH至5～7，补加水调节聚合物的质量浓度为45～55％。 (2) Preparation of the second polymer: 220.0 g of prenyl alcohol polyoxyethylene ether of molecular weight 5000 and 240 g of isobutylene polyoxyethylene ether of molecular weight 4000, 10.0 g of hydroxybutyl phosphate acrylate, 25.0 g of horse Leucic acid, 40.0 g of compound A (R 1 is -CH 2 , R 2 is H, n is 100) and 200.0 g of deionized water are added to the reaction vessel and mixed, hydrogen peroxide aqueous solution (including hydrogen peroxide 3.20 g, water 30.00 g), ascorbic acid Aqueous solution (including ascorbic acid 1.00g, water 30.00g), mercaptopropionic acid aqueous solution (including mercaptopropionic acid 2.75g, water 30.00g) The reaction temperature is normal temperature, the dropping time is 6.0h, and the temperature is kept for 1h after the dropping is completed. The copolymerization product is adjusted to pH 5-7 with alkali, and water is added to adjust the mass concentration of the polymer to 45-55%.
(3)将步骤(1)制得的第一聚合物和步骤(2)制得的第二聚合物按质量比1：3.5混合均匀，即得所述磷酸盐型聚羧酸减水剂。(3) The first polymer prepared in step (1) and the second polymer prepared in step (2) are uniformly mixed in a mass ratio of 1:3.5 to obtain the phosphate-type polycarboxylic acid water reducing agent.
按照GB/T8076-2008对实施例1至实施例4所制得的聚羧酸减水剂进行测试，折固掺量为0.12％时(相对于基准水泥用量)，减水率均高于40％，3d抗压强度比均大于170％，7d抗压强度比均大于150％，28d抗压强度比均大于145％，28d收缩率比均小于105％。According to GB/T8076-2008, the polycarboxylic acid water-reducing agents prepared in Examples 1 to 4 were tested, and when the amount of solid content is 0.12% (relative to the amount of benchmark cement), the water-reducing rate is higher than 40 %, 3d compressive strength ratio is greater than 170%, 7d compressive strength ratio is greater than 150%, 28d compressive strength ratio is greater than 145%, 28d shrinkage ratio is less than 105%.
分别采用基准和闽福P.O 42.5普通硅酸盐水泥，混凝土配合比为：水泥300kg/m 3、粉煤灰100kg/m 3、矿粉100kg/m 3、砂690kg/m 3、石子1050kg/m 3、水160kg/m 3，并添加膨润土3.5％(相对于水泥用量)，对实施例1到实施例4所制得的磷酸盐型聚羧酸减水剂和市售聚羧酸减水剂(PCE)进行性能测试，通过调整减水剂掺量，使得混凝土初始扩展度相当。 The benchmark and Minfu PO 42.5 ordinary Portland cement are adopted respectively, and the concrete mix ratio is: cement 300kg/m 3 , fly ash 100kg/m 3 , mineral powder 100kg/m 3 , sand 690kg/m 3 , stone 1050kg/m 3. Water 160kg/m 3 , and add 3.5% bentonite (relative to the amount of cement), the phosphate-type polycarboxylic acid water-reducing agent prepared in Examples 1 to 4 and the commercially available polycarboxylic acid water-reducing agent (PCE) Performance test, by adjusting the amount of water reducing agent, so that the initial expansion of concrete is equivalent.
表1基准水泥实施例性能对比Table 1 Performance comparison of benchmark cement examples
Figure PCTCN2019080745-appb-000004
Figure PCTCN2019080745-appb-000004
表2闽福水泥实施例性能对比Table 2 Minfu Cement Examples Performance Comparison
Figure PCTCN2019080745-appb-000005
Figure PCTCN2019080745-appb-000005
从表1和表2可以看出，对掺有膨润土的材料，本发明合成的磷酸盐型聚羧酸减水剂对比市售的聚羧酸减水剂(PCE)，减水率更大，保坍性能更好，由此可见本发明制备的聚羧酸减水剂对含泥量高的材料敏感性比较低，具有抗泥效果，同时本发明提供的磷酸盐型聚羧酸减水剂在不同水泥中均表现出良好的分散性、分散保持性，适应性更好，综合性能更优。As can be seen from Table 1 and Table 2, for the materials mixed with bentonite, the phosphate-type polycarboxylic acid water-reducing agent synthesized in the present invention has a greater water reduction rate than the commercially available polycarboxylic acid water-reducing agent (PCE). The slump retention performance is better, so it can be seen that the polycarboxylic acid water reducing agent prepared by the invention has relatively low sensitivity to materials with high mud content and has an anti-mud effect, and at the same time, the phosphate type polycarboxylic acid water reducing agent provided by the invention It shows good dispersibility and dispersion retention in different cements, better adaptability and better overall performance.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection of the present invention Within range.

Claims (10)

  1. 一种磷酸盐型聚羧酸减水剂，其特征在于，由第一聚合物和第二聚合物按质量比1:1～5混合制得；A phosphate type polycarboxylic acid water reducing agent, characterized in that it is prepared by mixing the first polymer and the second polymer in a mass ratio of 1:1 to 5;
    其中，所述第一聚合物按照由以下质量份数的原料反应制得：聚丙烯酸100～130份、聚乙二醇磷酸酯300～350份以及抗氧剂、催化剂；其中所述催化剂的用量为所述聚丙烯酸与所述聚乙二醇磷酸酯总质量的0.1％～1.0％，所述抗氧剂的用量为所述聚丙烯酸与所述聚乙二醇磷酸酯总质量的0.1％～1.0％；Wherein, the first polymer is prepared by reacting raw materials with the following mass parts: 100-130 parts of polyacrylic acid, 300-350 parts of polyethylene glycol phosphate, antioxidants, and catalyst; wherein the amount of the catalyst is It is 0.1% to 1.0% of the total mass of the polyacrylic acid and the polyethylene glycol phosphate, and the amount of the antioxidant is 0.1% to the total mass of the polyacrylic acid and the polyethylene glycol phosphate. 1.0%;
    所述第二聚合物按照由以下质量份数的原料反应制得：分子量为4000～6000的不饱和聚醚300～500份、不饱和磷酸酯5～18份、不饱和酸12～40份、化合物A 30～50份以及引发剂、分子量调节剂；其中所述引发剂的用量为聚醚单体总质量的0.1～3.0％，所述分子量调节剂的用量为聚醚单体总质量的0.1～2.0％，所述化合物A的结构式为：The second polymer is prepared by reacting raw materials with the following mass parts: 300-500 parts of unsaturated polyether with molecular weight of 4000-6000, 5-18 parts of unsaturated phosphate ester, 12-40 parts of unsaturated acid, 30-50 parts of compound A and initiator and molecular weight regulator; wherein the dosage of the initiator is 0.1-3.0% of the total mass of the polyether monomer, and the dosage of the molecular weight regulator is 0.1 of the total mass of the polyether monomer ~2.0%, the structural formula of the compound A is:
    Figure PCTCN2019080745-appb-100001
    Figure PCTCN2019080745-appb-100001
    其中，R 1为1～2个碳的烷基，R 2为H或CH 3，；n为20～100。 Among them, R 1 is an alkyl group of 1 to 2 carbons, R 2 is H or CH 3 ; n is 20 to 100.
  2. 制备方法，用于制备磷酸盐型聚羧酸减水剂，其特征在于：包括如下步骤：A preparation method for preparing a phosphate-type polycarboxylic acid water-reducing agent, which is characterized in that it includes the following steps:
    (1)制备第一聚合物：将质量分数为55％的聚丙烯酸加入反应容器中加热到50～70℃，在氮气保护下，再加入聚乙二醇磷酸酯、抗氧剂和催化剂；(1) Preparation of the first polymer: Polyacrylic acid with a mass fraction of 55% is added to the reaction vessel and heated to 50-70°C, and under the protection of nitrogen, polyethylene glycol phosphate, antioxidant and catalyst are added;
    温度升高到120～160℃，进行减压酯化反应；The temperature is increased to 120～160℃, and the reduced-pressure esterification reaction is carried out;
    压力降到80mbar，保温反应3～6h，期间抽除去水，反应结束后冷却至60～80℃，加入蒸馏水稀释，调节聚合物的质量浓度至45～55％；The pressure was reduced to 80 mbar, and the heat preservation reaction was carried out for 3 to 6 hours. During the reaction, water was pumped off. After the reaction was completed, it was cooled to 60 to 80°C. Diluted with distilled water to adjust the mass concentration of the polymer to 45 to 55%
    其中，所述聚丙烯酸与所述聚乙二醇磷酸酯质量比为100～130：300～350，所述催化剂的用量为聚丙烯酸与聚乙二醇磷酸酯总质量的0.1％～1.0％，所述抗氧剂的用量为聚丙烯酸与 聚乙二醇磷酸酯总质量的0.1％～1.0％；Wherein, the mass ratio of the polyacrylic acid to the polyethylene glycol phosphate is 100-130: 300-350, and the amount of the catalyst is 0.1%-1.0% of the total mass of the polyacrylic acid and polyethylene glycol phosphate. The amount of the antioxidant is 0.1% to 1.0% of the total mass of polyacrylic acid and polyethylene glycol phosphate;
    (2)制备第二聚合物：将分子量为4000～6000的不饱和聚醚、不饱和磷酸酯、不饱和酸、化合物A与去离子水加入反应容器中混合，将引发剂水溶液与分子量调节剂溶液滴入反应容器步进行反应，反应温度为10～60℃，滴加时间为2.0～8.0h，滴加完毕后保温0～2.0h；(2) Preparation of the second polymer: Add unsaturated polyether with molecular weight of 4000-6000, unsaturated phosphate ester, unsaturated acid, compound A and deionized water to the reaction vessel and mix them, and mix the initiator aqueous solution and molecular weight regulator The solution is dropped into the reaction vessel to carry out the reaction, the reaction temperature is 10 ~ 60 ℃, the dropping time is 2.0 ~ 8.0h, and the temperature is kept 0 ~ 2.0h after the drop is completed;
    制得共聚产物用碱调节pH至5～7，补加水调节共聚产物的质量浓度为45～55％；The obtained copolymer product is adjusted to pH 5-7 with alkali, and water is added to adjust the mass concentration of the copolymer product to 45-55%;
    其中，所述不饱和聚醚、所述不饱和磷酸酯、所述不饱和酸、所述化合物A的质量比为300～500：5～18：12～40：30～50，引发剂的用量为聚醚单体总质量的0.1～3.0％，分子量调节剂的用量为聚醚单体总质量的0.1～2.0％；所述化合物A的结构式为：Wherein, the mass ratio of the unsaturated polyether, the unsaturated phosphate ester, the unsaturated acid, and the compound A is 300-500: 5-18: 12-40: 30-50, and the amount of initiator used It is 0.1-3.0% of the total mass of the polyether monomer, and the amount of the molecular weight regulator is 0.1-2.0% of the total mass of the polyether monomer; the structural formula of the compound A is:
    Figure PCTCN2019080745-appb-100002
    Figure PCTCN2019080745-appb-100002
    其中，R 1为1～2个碳的烷基，R 2为H或CH 3，；n为20～100； Among them, R 1 is an alkyl group of 1 to 2 carbons, R 2 is H or CH 3 ; n is 20 to 100;
    (3)将所述第一聚合物和所述第二聚合物按1:1～5的质量比混合均匀，获得所述磷酸盐型聚羧酸减水剂。(3) The first polymer and the second polymer are uniformly mixed in a mass ratio of 1:1 to 5 to obtain the phosphate-type polycarboxylic acid water-reducing agent.
  3. 如权利要求2所述的制备方法，其特征在于，所述催化剂为乙基磺酸、苯磺酸、对甲苯磺酸和98％的浓硫酸中的至少一种。The preparation method according to claim 2, wherein the catalyst is at least one of ethylsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and 98% concentrated sulfuric acid.
  4. 如权利要求2所述的制备方法，其特征在于，所述聚乙二醇磷酸酯为聚乙二醇(800)磷酸酯。The preparation method according to claim 2, wherein the polyethylene glycol phosphate is polyethylene glycol (800) phosphate.
  5. 如权利要求2所述的制备方法，其特征在于，所述分子量为4000～6000的不饱和聚醚包括异丁烯醇聚氧乙烯醚和烯丙基聚氧乙烯醚，或者包括异丁烯醇聚氧乙烯醚和异戊烯醇聚氧乙烯醚，或者包括异丁烯醇聚氧乙烯醚。The preparation method according to claim 2, wherein the unsaturated polyether with a molecular weight of 4000-6000 includes isobutylene alcohol polyoxyethylene ether and allyl polyoxyethylene ether, or includes isobutylene alcohol polyoxyethylene ether And prenyl alcohol polyoxyethylene ether, or including isobutylene alcohol polyoxyethylene ether.
  6. 如权利要求2所述的制备方法，其特征在于，所述不饱和酸为丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸、衣康酸酐中的一种。The preparation method according to claim 2, wherein the unsaturated acid is one of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride.
  7. 如权利要求2所述的制备方法，其特征在于，所述不饱和磷酸酯为甲基丙烯酸羟丁 基磷酸酯或丙烯酸羟丁基磷酸酯。The preparation method according to claim 2, wherein the unsaturated phosphate ester is hydroxybutyl methacrylate or hydroxybutyl phosphate acrylate.
  8. 如权利要求2所述的制备方法，其特征在于，所述引发剂为水溶性无机过氧类引发剂或水溶性氧化还原引发体系。The preparation method according to claim 2, wherein the initiator is a water-soluble inorganic peroxy initiator or a water-soluble redox initiator system.
  9. 如权利要求8所述的制备方法，其特征在于，所述水溶性无机过氧类引发剂为过硫酸铵、过硫酸钾中的至少一种；所述水溶性氧化还原引发体系为双氧水-吊白块、双氧水-抗坏血酸和过硫酸盐-亚硫酸氢钠中的至少一种。The preparation method according to claim 8, wherein the water-soluble inorganic peroxy initiator is at least one of ammonium persulfate and potassium persulfate; the water-soluble redox initiator system is hydrogen peroxide-pendant At least one of white block, hydrogen peroxide-ascorbic acid, and persulfate-sodium bisulfite.
  10. 如权利要求9所述的制备方法，其特征在于，所述分子量调节剂为巯基乙酸、巯基丙酸、巯基乙醇、异丙醇、乙酸钠和十二硫醇中的至少一种。The preparation method according to claim 9, wherein the molecular weight regulator is at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium acetate, and dodecanethiol.
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