WO2021226869A1 - 一种固体聚羧酸减水剂及其制备方法 - Google Patents

一种固体聚羧酸减水剂及其制备方法 Download PDF

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WO2021226869A1
WO2021226869A1 PCT/CN2020/090002 CN2020090002W WO2021226869A1 WO 2021226869 A1 WO2021226869 A1 WO 2021226869A1 CN 2020090002 W CN2020090002 W CN 2020090002W WO 2021226869 A1 WO2021226869 A1 WO 2021226869A1
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Prior art keywords
reducing agent
polycarboxylic acid
preparation
acid water
water reducing
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PCT/CN2020/090002
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English (en)
French (fr)
Inventor
朱建民
刘兆滨
董振鹏
杨雪
张建东
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辽宁奥克化学股份有限公司
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Priority to DE112020007177.4T priority Critical patent/DE112020007177T5/de
Priority to PCT/CN2020/090002 priority patent/WO2021226869A1/zh
Publication of WO2021226869A1 publication Critical patent/WO2021226869A1/zh

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    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/32—Superplasticisers
    • 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

Definitions

  • the invention relates to the field of concrete admixtures, in particular to a solid polycarboxylic acid water reducing agent and a preparation method thereof.
  • Water reducer is an indispensable part in today's concrete industry, starting from the first generation of lignosulfonate series of ordinary water reducing agents, to the second generation of naphthalene-based water-reducing agents, melamine-based water-reducing agents, and amino High-efficiency water-reducing agents such as sulfonate-based water-reducing agents and fatty acid-based water-reducing agents, and to the current third-generation polycarboxylic acid-based high-performance water-reducing agents, each water-reducing agent has its own unique advantages; In particular, the polycarboxylic acid-based high-performance water-reducing agent is the most widely used concrete in today's concrete, and it has its presence in major projects.
  • the polycarboxylic acid-based water-reducing agents on the market are mainly mother liquor water agents, and the solid content of the product is generally about 40%-50%, which will increase the cost during transportation.
  • the application in engineering construction is restricted.
  • the mother liquor of water reducing agent can be directly converted into powder polycarboxylic acid by spray drying method, the spray drying method has high energy consumption, and some products will be lost during drying and production. Security Question.
  • CN108192041A discloses a preparation method and application of a powdered polycarboxylic acid water reducing agent, the preparation of a benzene ring-containing polycarboxylic acid water reducing agent and how to spray and dry it into a powdered polycarboxylic acid water reducing agent Method and application.
  • the preparation method includes: preparing a polycarboxylic acid monomer a, a small benzene ring-containing monomer b, and a benzene ring-containing polyether monomer c in an aqueous medium through free radical copolymerization to obtain a polycarboxylic acid water reducing agent Mother liquor; the polycarboxylic acid water-reducing agent mother liquor is directly passed through the centrifugal atomizer of the sprayer to form droplets without adding a release agent.
  • the average particle size of the powder is controlled to be 50-150um, and the droplets are dried after entering the drying chamber
  • the material is turned into powder, and the material is led to the discharge port through the induced draft fan, and the material is packaged and discharged by the bag packaging machine to obtain the powdery polyshuttle acid water reducing agent.
  • the invention will have a certain loss during the spray centrifugation process, and spray drying requires a higher temperature, and the energy consumption requirement under the same output is too high.
  • CN108484841A discloses a method for preparing a solid sheet-like polycarboxylic acid water-reducing agent by bulk polymerization.
  • the solid sheet-like polycarboxylic acid water-reducing agent is prepared by bulk polymerization, and a certain amount of just synthesized liquid polyether is monohydrated.
  • the process is relatively complicated in the synthesis process, and the higher reaction temperature causes a great loss of energy consumption.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a solid polycarboxylic acid water reducing agent with good workability and low production and transportation costs.
  • a preparation method of solid polycarboxylic acid water reducing agent including:
  • the mixed solution is subjected to aging treatment, and then cooled and solidified to obtain the solid polycarboxylic acid water reducing agent.
  • the added amount of the polyether monomer is 82-89%, the added amount of the hyperbranched monomer is 0.4-3%, and the unsaturated carboxylic acid
  • the addition amount of the chain transfer agent is 7-11%, the addition amount of the chain transfer agent is 0.2-0.7%, and the addition amount of the initiator is 0.4-1.5%.
  • the polyether monomer is selected from one or more of methallyl polyoxyethylene ether, prenol polyoxyethylene ether and hydroxybutyl polyoxyethylene ether, and The molecular weight of the polyether monomer is 1200-5000, preferably 2000-4000.
  • the hyperbranched monomer has a structure as shown in Formula I, wherein n is an integer from 1 to 15, m is an integer from 1 to 10, x is an integer from 1 to 10, and y is from 1 to 1. An integer of 10.
  • the initiator is selected from benzoyl peroxide, lauryl peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, One or more of azobisisovaleronitrile, azobiscyclohexylcarbonitrile, dimethyl azodiisobutyrate, dicyclohexyl peroxydicarbonate, and hexadecyl peroxydicarbonate.
  • the unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, maleic acid, and fumaric acid.
  • the chain transfer agent is selected from sodium methacrylate sulfonate, sodium allyl sulfonate, thioglycolic acid, mercaptopropionic acid, mercaptoethanol, n-dodecyl mercaptan, sodium hypophosphite, ethylene One or more of sodium sulfonate, sodium propenyl sulfonate and sodium styrene sulfonate.
  • the unsaturated carboxylic acid and the chain transfer agent are added to the liquid by dropping, and the dropping time is 0.5-2h.
  • the aging treatment time is 0.5-3h.
  • the present invention provides a solid polycarboxylic acid water reducing agent, which is prepared according to the above method.
  • the solid polycarboxylate water-reducing agent of the present invention Due to the addition of hyperbranched monomers, the solid polycarboxylate water-reducing agent of the present invention has reduced requirements for viscosity during polymerization, and has good workability to concrete in the process of concrete evaluation, without bleeding, bleeding, or bleeding. Phenomena such as stone leakage can reduce the viscosity of concrete under the condition of low water-cement ratio.
  • the method of the present invention can obtain an anhydrous solid polycarboxylic acid water reducing agent product after the preparation is completed, and it does not need to be spray-dried like the traditional mother liquor water agent to obtain the powder polycarboxylic acid water reducing agent, and the powder polycarboxylic acid water reducing agent Compared with the agent, the production cost and the long-distance transportation cost are greatly reduced.
  • the invention provides a preparation method of a solid polycarboxylic acid water reducing agent, which comprises the following steps:
  • the mixed solution is subjected to aging treatment, and then cooled and solidified to obtain the solid polycarboxylic acid water reducing agent.
  • the added amount of the polyether monomer is 82-89%, the added amount of the hyperbranched monomer is 0.4-3%, and the added amount of the unsaturated carboxylic acid is 7- 11%, the added amount of the chain transfer agent is 0.2-0.7%, and the added amount of the initiator is 0.4-1.5%.
  • the polyether monomer and the hyperbranched monomer first melt into a liquid within a certain temperature range.
  • the polyether monomer can be completely melted first, and then the hyperbranched monomer is added to melt.
  • the temperature of the chemical material can be controlled at 65-100°C.
  • the polyether monomer used in the present invention is selected from one or more of methallyl polyoxyethylene ether, prenol polyoxyethylene ether and hydroxybutyl polyoxyethylene ether, and the polyether monomer
  • the molecular weight is 1200-5000, preferably 2000-4000.
  • the hyperbranched monomer used in the present invention is a polymer obtained by adding polyvinyl polyamine as a raw material to random blocks of ethylene oxide and propylene oxide. It has a structure as shown in formula I, where n represents epoxy The addition number of ethane (EO), which is an integer of 1-15, preferably an integer of 3-10, m represents the addition number of propylene oxide (PO), which is an integer of 1-10, preferably 2 An integer of -6, x is an integer of 1-10, and y is an integer of 1-10.
  • EO epoxy
  • EO addition number of ethane
  • PO propylene oxide
  • x is an integer of 1-10
  • y is an integer of 1-10.
  • the initiator used in the present invention is an oil-soluble initiator, which is selected from the group consisting of benzoyl peroxide and ten Diacyl, ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobiscyclohexylcarbonitrile, azobisisobutyric acid
  • the stirring time is usually 5-10min.
  • the unsaturated carboxylic acid and the chain transfer agent can be mixed first and then added at the same time. 0.5-2h.
  • the unsaturated carboxylic acid used in the present invention is selected from one or more of acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, maleic acid and fumaric acid.
  • the chain transfer agent used in the present invention is selected from sodium methacrylate sulfonate, sodium allyl sulfonate, thioglycolic acid, mercaptopropionic acid, mercaptoethanol, n-dodecyl mercaptan, sodium hypophosphite, sodium vinyl sulfonate , One or more of sodium propenyl sulfonate and sodium styrene sulfonate.
  • the temperature is lowered to about 60°C and the material is discharged, and the anhydrous solid polycarboxylic acid water reducing agent can be obtained when the product is solidified at room temperature.
  • the solid polycarboxylic acid water-reducing agent prepared by the present invention can be prepared by adding water to the solid polycarboxylic acid water-reducing agent into liquids of different concentrations or further processed into powdered solid polycarboxylic acid water-reducing agent according to different construction requirements.
  • the solid polycarboxylic acid water-reducing agent can be directly mixed into dry-mixed mortar or sprayed concrete for use. The original performance of the water-reducing agent will not be reduced during the change of the shape.
  • the solid polycarboxylic acid water-reducing agent of the present invention Due to the addition of hyperbranched monomers, the solid polycarboxylic acid water-reducing agent of the present invention has reduced requirements for viscosity during polymerization, and at the same time, its state is stable, and no adhesion occurs when stored at room temperature.
  • the solid polycarboxylic acid water-reducing agent of the present invention has excellent water-reducing and dispersing effect, and has good workability to concrete in the process of concrete evaluation. It exhibits good fluidity and retention ability, maintains excellent workability at different dosages, and shows strong adaptability to different types of cement.
  • the preparation process of the present invention can directly obtain anhydrous solid polycarboxylic acid water-reducing agent products, and does not need to be spray-dried like the traditional mother liquor water agent to obtain the powder polycarboxylic acid water-reducing agent.
  • the mother liquor of carboxylic acid water reducer is simple and has a short cycle, and is more convenient in operation.
  • the product has more obvious advantages in transportation distance and transportation cost.
  • polyether thermal materials can be used to produce solid polycarboxylic acid water reducer, the total cost can be saved. About 30%, which greatly improves the energy saving and consumption reduction of water reducing agent manufacturers.
  • the overall process of the preparation method of the present invention is green and environmentally friendly, is conducive to industrialized production and industrialized promotion and application, and has good economic benefits and social significance.
  • anhydrous solid polycarboxylic acid water reducing agent After adding initiator 2g azobisisobutyronitrile, 2.5g azobisisovaleronitrile, stirring for 10min, start to add dropwise a mixture of 36.2g methacrylic acid, 2.3g sodium hypophosphite, control the dripping reaction time in 1.5h ⁇ 5min, aging for 2.5h after the end of the reaction, pour into the tray after the end of aging, and after the product solidifies, an anhydrous solid polycarboxylic acid water reducing agent can be obtained.
  • hydroxybutyl polyoxyethylene ether (theoretical molecular weight is 2400) is put into the reactor, and the temperature is raised to 75°C. After the material is completely melted into a liquid state, 6g of the hyperbranched monomer 3 obtained in the preparation example is added and the stirring is continued for 10 minutes . After adding initiator 3.8g ammonium persulfate, stirring for 10min, start to add dropwise feeding by a mixture of 30.9g methacrylic acid and 3g sodium methacrylic acid sulfonate, control the dripping reaction time within 1h ⁇ 5min, and aging after the reaction is over 2.5h, after the aging is finished, pour it into the tray and discharge it. After the product is solidified, an anhydrous solid polycarboxylic acid water reducing agent can be obtained.
  • the comparative example is only that the hyperbranched monomer is not added under the same conditions as the example, and the molecular weight of the sample of example 1-8 and the comparative example 1-8 (without hyperbranched monomer added) are tested by gel liquid chromatography. ) The molecular weight of the sample, and the results are shown in Table 1.
  • the viscosity of the sample after adding the hyperbranched monomer is generally between 3000-3500, and the viscosity without the hyperbranched monomer is generally between 4900-5500, and the molecular weight of the solid polycarboxylic acid water-reducing agent is not large. Change; it is proved that adding hyperbranched monomers can significantly reduce the viscosity of solid polycarboxylic acid water-reducing agent.
  • the decrease in viscosity indicates that the equipment requirements of solid polycarboxylic acid water-reducing agent in the production have been reduced, and the production will be increased when the product is sliced There is improvement, and there is more room for improvement in product profit.
  • the solid polycarboxylic acid water-reducing agent prepared in Examples 1-8 is configured as a water-reducing agent with a concentration of 10%. According to the test requirements of the high-performance water-reducing agent in the GB8076-2008 "Concrete Additives" standard, the examples are synthesized The performance of the sample and the commercial water reducer (HD-14 high-performance polycarboxylic acid water reducer produced by Shenyang Haida Building Material Factory) was compared. The experimental formulation is shown in Table 2, and the concrete performance test results are shown in Tables 3 and 4. Shown.

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Abstract

本发明提供一种固体聚羧酸减水剂及其制备方法，该制备方法包括：将聚醚单体与超支化单体融化成液体；向所述液体中加入引发剂并搅拌，之后加入不饱和羧酸和链转移剂，得到混合溶液；以及对所述混合溶液进行老化处理，之后降温凝固，得到所述固体聚羧酸减水剂。本发明的固体聚羧酸减水剂由于加入了超支化单体，在聚合时对粘度的要求有所降低，并在混凝土评价过程中对混凝土和易性较好，无泌水、泌浆、漏石等现象，在低水灰比条件下能够降低混凝土粘度，此外，本发明的方法制备结束即得到无水固体聚羧酸减水剂产品，无需像传统母液水剂需经过喷雾干燥才能得到粉体聚羧酸减水剂，与粉体聚羧酸减水剂相比大大的减少了生产成本以及长途运输成本。

Description

一种固体聚羧酸减水剂及其制备方法 技术领域
本发明涉及混凝土外加剂领域，特别涉及一种固体聚羧酸减水剂及其制备方法。
背景技术
减水剂在当今混凝土行业中是不可或缺的重要部分，从第一代木质素磺酸盐系列普通减水剂开始，到第二代萘系减水剂、密胺系减水剂、氨基磺酸盐系减水剂、脂肪酸系减水剂等高效减水剂，再到现在的第三代聚羧酸系高性能减水剂，每一种减水剂都有它自身的独特优势；尤其是聚羧酸系高性能减水剂是当今混凝土中应用最多的一种，在各大工程上均有它的身影。
但目前市场上多数聚羧酸系减水剂都以母液水剂为主，产品固含量一般在40％-50％左右，这样在运输中就会使成本增加，而且在喷射混凝土与干混砂浆等工程施工中应用受到限制，虽然现在可以用喷雾干燥方法将减水剂母液直接转化为粉体聚羧酸，但喷雾干燥法存在高能耗、产品会有部分产品在干燥中损失及生产中的安全问题。
CN108192041A公开了一种粉末状聚羧酸减水剂的制备方法及应用，所述一种含苯环的聚羧酸减水剂的制备及如何喷雾干燥后成粉末状聚羧酸减水剂的方法及应用，制备方法包括:由聚羧酸单体a、含苯环小单体b、含苯环聚醚单体c在水性介质中通过自由基共聚反应制备，得到聚羧酸减水剂母液；将所述聚羧酸减水剂母液，直接通过喷雾机的离心式雾化器形成雾滴，无需添加隔离剂，控制粉末的平均粒径在50-150um,雾滴进入干燥室后干燥成粉末，通过引风机将物料引到出料口，采用袋装包装机包装出料，得到粉末状聚梭酸减水剂。该发明在喷雾离心过程中会有一定的损失，并且喷雾干燥要求温度较高，相同产量下能耗需求量过高。
CN108484841A公开了一种本体聚合的固片状聚羧酸减水剂的制备方法，所述一种采用本体聚合制备固片状聚羧酸减水剂，将一定量的刚刚合成的液态聚醚单体和降粘剂加入到反应釜中，搅拌加热；控制温度在100-105℃，开始加入一定量初始引发剂、有机过氧类引发剂、增溶剂、链转移剂、初始引发剂；5min后，开始滴加小单体溶液，小单体溶液滴加时间为a小时，小单体溶液由一定比例的氟代功能单体和丙烯酸组成；小单体溶液滴加 10min后，向釜中投入一定量的有机过氧类引发剂，之后每隔10min投入一次，直到小单体溶液滴加完成前投入完最后一次；滴加结束后，将温到度升到在110-115℃，保持温度恒定，熟化b小时，之后冷却切片封装，既得固片状聚羧酸减水剂。该发明在合成过程中工艺相对较复杂，而且反应温度较高对能耗损失很大。
需注意的是，前述背景技术部分公开的信息仅用于加强对本发明的背景理解，因此它可以包括不构成对本领域普通技术人员已知的现有技术的信息。
发明内容
本发明的目的在于克服现有技术的不足，提供一种具有良好和易性且生产及运输成本均较低的固体聚羧酸减水剂。
为了实现上述目的，本发明采用如下技术方案：
一种固体聚羧酸减水剂的制备方法，包括：
将聚醚单体与超支化单体融化成液体；
向所述液体中加入引发剂并搅拌，之后加入不饱和羧酸和链转移剂，得到混合溶液；以及
对所述混合溶液进行老化处理，之后降温凝固，得到所述固体聚羧酸减水剂。
在一些实施例中，按各原料的总质量计，所述聚醚单体的加入量为82-89％，所述超支化单体的加入量为0.4-3％，所述不饱和羧酸的加入量为7-11％，所述链转移剂的加入量为0.2-0.7％，所述引发剂的加入量为0.4-1.5％。
在一些实施例中，所述聚醚单体选自甲基烯丙基聚氧乙烯醚、异戊烯醇聚氧乙烯醚和羟丁基聚氧乙烯基醚中的一种或多种，且所述聚醚单体的分子量为1200-5000，优选为2000-4000。
在一些实施例中，所述超支化单体具有如式Ⅰ所示的结构，其中n为1-15的整数，m为1-10的整数，x为1-10的整数，y为1-10的整数。
Figure PCTCN2020090002-appb-000001
在一些实施例中，所述引发剂选自过氧化苯甲酰、过氧化十二酰、过硫酸铵、过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异庚腈、偶氮二异戊腈、偶氮二环己基甲腈、偶氮二异丁酸二甲酷、过氧化二碳酸二环己酷和过氧化二碳酸二十六酯中的一种或多种。
在一些实施例中，所述不饱和羧酸选自丙烯酸、甲基丙烯酸、衣康酸、马来酸酐、马来酸和富马酸中的一种或多种。
在一些实施例中，所述链转移剂选自甲基丙烯磺酸钠、烯丙基磺酸钠、巯基乙酸、巯基丙酸、巯基乙醇、正十二烷基硫醇、次磷酸钠、乙烯基磺酸钠、丙烯基磺酸钠和苯乙烯磺酸钠中的一种或多种。
在一些实施例中，不饱和羧酸和链转移剂通过滴加的方法加入所述液体中，所述滴加的时间为0.5-2h。
在一些实施例中，所述老化处理的时间为0.5-3h。
另一方面，本发明提供一种固体聚羧酸减水剂，其是根据上述方法制备得到。
本发明的固体聚羧酸减水剂由于加入了超支化单体，在聚合时对粘度的要求有所降低，并在混凝土评价过程中对混凝土和易性较好，无泌水、泌浆、漏石等现象，在低水灰比条件下能够降低混凝土粘度。此外，本发明的方法制备结束即得到无水固体聚羧酸减水剂产品，无需像传统母液水剂需经过喷雾干燥才能得到粉体聚羧酸减水剂，与粉体聚羧酸减水剂相比大大的减少了生产成本以及长途运输成本。
具体实施方式
下面根据具体实施例对本发明的技术方案做进一步说明。本发明的保护范围不限于以下实施例，列举这些实例仅出于示例性目的而不以任何方式限制本发明。
本发明提供了一种固体聚羧酸减水剂的制备方法，其包括以下步骤：
将聚醚单体与超支化单体融化成液体；
向所述液体中加入引发剂并搅拌，之后加入不饱和羧酸和链转移剂，得到混合溶液；以及
对所述混合溶液进行老化处理，之后降温凝固，得到所述固体聚羧酸减水剂。
按各原料的总质量计，所述聚醚单体的加入量为82-89％，所述超支化单体的加入量为0.4-3％，所述不饱和羧酸的加入量为7-11％，所述链转移剂的加入量为0.2-0.7％，所述引发剂的加入量为0.4-1.5％。
聚醚单体与超支化单体首先在一定温度范围内融化成液体，可首先将聚醚单体完全融 化，之后再加入超支化单体进行融化。化料的温度可控制在65-100℃。
本发明所用的聚醚单体选自甲基烯丙基聚氧乙烯醚、异戊烯醇聚氧乙烯醚和羟丁基聚氧乙烯基醚中的一种或多种，且聚醚单体的分子量为1200-5000，优选为2000-4000。
本发明所用的超支化单体是以多乙烯多胺为原料加入环氧乙烷与环氧丙烷无规嵌段后所得的聚合物，其具有如式Ⅰ所示的结构，其中n表示环氧乙烷(EO)的加成数，其为1-15的整数，优选为3-10的整数，m表示环氧丙烷(PO)的加成数，其为1-10的整数，优选为2-6的整数，x为1-10的整数，y为1-10的整数。
Figure PCTCN2020090002-appb-000002
聚醚单体与超支化单体均融化成液体后，需向该液体中加入引发剂并搅拌，本发明所用的引发剂为油溶性引发剂，其选自过氧化苯甲酰、过氧化十二酰、过硫酸铵、过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异庚腈、偶氮二异戊腈、偶氮二环己基甲腈、偶氮二异丁酸二甲酷、过氧化二碳酸二环己酷和过氧化二碳酸二十六酯中的一种或多种，搅拌的时间通常为5-10min。
加入引发剂并搅拌后，向液体中加入不饱和羧酸和链转移剂，不饱和羧酸和链转移剂可先混合后再同时加入，并优选采用滴加的方式进行，滴加的时间为0.5-2h。
本发明所用的不饱和羧酸选自丙烯酸、甲基丙烯酸、衣康酸、马来酸酐、马来酸和富马酸中的一种或多种。
本发明所用的链转移剂选自甲基丙烯磺酸钠、烯丙基磺酸钠、巯基乙酸、巯基丙酸、巯基乙醇、正十二烷基硫醇、次磷酸钠、乙烯基磺酸钠、丙烯基磺酸钠和苯乙烯磺酸钠中的一种或多种。
加入不饱和羧酸和链转移剂后，得到混合溶液，并在一定恒温条件下持续搅拌对该混合溶液进行老化处理，老化处理的时间为0.5-3h。
老化处理后，降温至60℃左右出料，在室温下待产品凝固即可得到无水固体聚羧酸减水剂。
本发明所制得的固体聚羧酸减水剂可根据不同施工需求将固体聚羧酸减水剂加水配 置成不同浓度的液体或进一步加工制成粉末状固体聚羧酸减水剂，粉末状固体聚羧酸减水剂可以直接掺入干混砂浆或喷射混凝土中使用，形态发生变化过程中，并不会降低减水剂原本性能。
本发明的固体聚羧酸减水剂由于加入了超支化单体，在聚合时对粘度的要求有所降低，同时其状态稳定，室温存放下不会出现粘结。本发明的固体聚羧酸减水剂具有优异的减水分散效果，在混凝土评价过程中对混凝土和易性较好，无泌水、泌浆、漏石等现象，在低掺量下仍能表现出较好的流动性、保持能力，在不同掺量下均能保持优良的和易性，并且对不同品种的水泥表现出很强的适应性。
此外，本发明的制备工艺可直接得到无水固体聚羧酸减水剂产品，无需像传统母液水剂需经过喷雾干燥才能得到粉体聚羧酸减水剂，生产工艺及生产周期比传统聚羧酸减水剂母液简单且周期短，操作上更为便捷，产品在运输距离及运输成本优势更加明显，同时若能使用聚醚热物料来生产固体聚羧酸减水剂，总成本能节约30％左右，对于减水剂厂家节能降耗有很大的提升。
因此，本发明的制备方法整体工艺绿色环保，有利于工业化生产及工业化推广应用，具有很好的经济效益和社会意义。
以下通过具体实施例来对本发明作进一步说明，这些实施例描述了较佳的实施方案，但并非构成对本发明的限制，任何熟悉本专业的技术人员可能利用上述涉及的发明内容加以变更为同等变化的等效实施例。
实施例
制备例 超支化单体的合成
在0.3L干燥的不锈钢高压反应釜中40g多乙烯多胺，催化剂0.2g，密闭反应釜通入氮气置换3次，升温至120℃，缓慢向反应釜同时加入29.34g环氧乙烷与23.2g环氧丙烷，通料过程中维持反应温度120-130℃，压力0.3-0.4MPa，待通料完毕后120℃持续搅拌1h，然后冷却至75-80℃左右出料，即可得超支化单体。
实施例1
首先将350g甲基烯丙基聚氧乙烯醚(理论分子量为2400)投入反应器中，升温至70℃，待物料完全融化成液态后，加入3.5g制备例得到的超支化单体后继续搅拌10min，再加入引发剂3.5g过氧化苯甲酰，搅拌10min后开始滴加由37.5g丙烯酸、2g巯基乙酸的 混合滴加料，控制滴加反应时间在1h±5min，反应结束后升温至75℃老化2h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
实施例2
首先将357g甲基烯丙基聚氧乙烯醚(理论分子量为3000)投入反应器中，升温至75℃，待物料完全融化成液态后，加入4g制备例得到的超支化单体后继续搅拌10min，在加入引发剂3.6g过氧化苯甲酰，搅拌10min后开始滴加由37.9g丙烯酸、2.2g次磷酸钠的混合滴加料，控制滴加反应时间在1h±5min，反应结束后老化2h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
实施例3
首先将351g甲基烯丙基聚氧乙烯醚(理论分子量为3000)投入反应器中，升温至75℃，待物料完全融化成液态后，加入5g制备例得到的超支化单体后继续搅拌10min，在加入引发剂4g偶氮二异丁腈，搅拌10min后开始滴加由35.3g丙烯酸、1.5g巯基丙酸、0.7g巯基乙醇的混合滴加料，控制滴加反应时间在1h±5min，反应结束后老化2h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
实施例4
首先将345g异戊烯醇聚氧乙烯醚(理论分子量为2400)投入反应器中，升温至75℃，待物料完全融化成液态后，加入5g制备例得到的超支化单体后继续搅拌10min，在加入引发剂4g偶氮二异丁腈，搅拌10min后开始滴加由40.2g甲基丙烯酸、2.3g次磷酸钠的混合滴加料，控制滴加反应时间在1.5h±5min，反应结束后老化2.5h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
实施例5
首先将326g异戊烯醇聚氧乙烯醚(理论分子量为3000)投入反应器中，升温至70℃，待物料完全融化成液态后，加入6g制备例得到的超支化单体后继续搅拌10min，在加入引发剂2g偶氮二异丁腈、2.5g偶氮二异戊腈，搅拌10min后开始滴加由36.2g甲基丙烯酸、2.3g次磷酸钠的混合滴加料，控制滴加反应时间在1.5h±5min，反应结束后老化2.5h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
实施例6
首先将364g羟丁基聚氧乙烯基醚(理论分子量为2400)投入反应器中，升温至75℃，待物料完全融化成液态后，加入6g制备例得到的超支化单体3后继续搅拌10min，在加入引发剂3.8g过硫酸铵，搅拌10min后开始滴加由30.9g甲基丙烯酸、3g甲基丙烯磺酸钠的混合滴加料，控制滴加反应时间在1h±5min，反应结束后老化2.5h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
实施例7
首先将350g羟丁基聚氧乙烯基醚(理论分子量为3000)投入反应器中，升温至75℃，待物料完全融化成液态后，加入3g制备例得到的超支化单体后继续搅拌10min，在加入引发剂3.8g过硫酸铵，搅拌10min后开始滴加由30.9g甲基丙烯酸、3g甲基丙烯磺酸钠的混合滴加料，控制滴加反应时间在1h±5min，反应结束后老化2.5h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
实施例8
首先将342g羟丁基聚氧乙烯基醚(理论分子量为3600)投入反应器中，升温至80℃，待物料完全融化成液态后，加入4g制备例得到的超支化单体后继续搅拌10min，在加入引发剂3.5g偶氮二异丁腈，搅拌5min后开始滴加由32.7g甲基丙烯酸、7g衣康酸、1g巯基丙酸、0.7g巯基乙醇的混合滴加料，控制滴加反应时间在1h±5min，反应结束后老化2h，老化结束后倒入托盘出料，待产品凝固后可得到无水固体聚羧酸减水剂。
将实施例1-8制备出来的固体聚羧酸减水剂统一放入烘箱中融化，使用石油产品运动粘度测定仪在70℃条件下用粘度计测试实施例1-8样品粘度及对比例1-8的粘度，其中对比例仅仅是在实施例相同条件下未加入超支化单体，并用凝胶液相色谱测试实施例1-8样品分子量及对比例1-8(未加超支化单体)样品的分子量，结果如表1所示。
表1实施例和对比例制备的固体聚羧酸减水剂的粘度及分子量对比
Figure PCTCN2020090002-appb-000003
通过测试得出结论：加入超支化单体后样品粘度普遍3000-3500之间，未加超支化单体粘度普遍在4900-5500之间，并且固体聚羧酸减水剂产品分子量未有较大变化；证明加入超支化单体对固体聚羧酸减水剂粘度有明显降低，粘度的降低表明固体聚羧酸减水剂在生产中对设备要求有所减低，对产品成型切片中会使产量有提升，对产品利润有更多的提升空间。
将实施例1-8制备出来的固体聚羧酸减水剂配置成10％浓度的减水剂，按照GB8076-2008《混凝土外加剂》标准中高性能减水剂的测试要求，将实施例中合成的样品与市售减水剂(沈阳海达建材厂生产的HD-14高性能聚羧酸减水剂)进行性能对比，实验配比如表2所示，混凝土性能测试结果如表3和表4所示。
表2混凝土试验配比(kg/m 3)
Figure PCTCN2020090002-appb-000004
表3千山水泥42.5的混凝土性能测试结果
Figure PCTCN2020090002-appb-000005
表4海螺水泥42.5的混凝土性能测试结果
Figure PCTCN2020090002-appb-000006
通过上述实验结果表明，本发明制得的固体聚羧酸减水剂对不同品种的水泥适应性良好，相对传统聚羧酸减水剂母液具有更高的减水率以及保持性能，而且本发明加入超支化 单体对产品粘度有所降低及混凝土泌水率，无明显泌水、泌浆、漏石，对混凝土和易性有一定改善。
本领域技术人员应当注意的是，本发明所描述的实施方式仅仅是示范性的，可在本发明的范围内作出各种其他替换、改变和改进。因而，本发明不限于上述实施方式，而仅由权利要求限定。

Claims (10)

  1. 一种固体聚羧酸减水剂的制备方法，其特征在于，包括：
    将聚醚单体与超支化单体融化成液体；
    向所述液体中加入引发剂并搅拌，之后加入不饱和羧酸和链转移剂，得到混合溶液；以及
    对所述混合溶液进行老化处理，之后降温凝固，得到所述固体聚羧酸减水剂。
  2. 根据权利要求1所述的制备方法，其特征在于，按各原料的总质量计，所述聚醚单体的加入量为82-89％，所述超支化单体的加入量为0.4-3％，所述不饱和羧酸的加入量为7-11％，所述链转移剂的加入量为0.2-0.7％，所述引发剂的加入量为0.4-1.5％。
  3. 根据权利要求1所述的制备方法，其特征在于，所述聚醚单体选自甲基烯丙基聚氧乙烯醚、异戊烯醇聚氧乙烯醚和羟丁基聚氧乙烯基醚中的一种或多种，且所述聚醚单体的分子量为1200-5000，优选为2000-4000。
  4. 根据权利要求1所述的制备方法，其特征在于，所述超支化单体具有如式Ⅰ所示的结构，其中n为1-15的整数，m为1-10的整数，x为1-10的整数，y为1-10的整数。
    Figure PCTCN2020090002-appb-100001
  5. 根据权利要求1所述的制备方法，其特征在于，所述引发剂选自过氧化苯甲酰、过氧化十二酰、过硫酸铵、过硫酸钾、过硫酸钠、偶氮二异丁腈、偶氮二异庚腈、偶氮二异戊腈、偶氮二环己基甲腈、偶氮二异丁酸二甲酷、过氧化二碳酸二环己酷和过氧化二碳酸二十六酯中的一种或多种。
  6. 根据权利要求1所述的制备方法，其特征在于，所述不饱和羧酸选自丙烯酸、甲基丙烯酸、衣康酸、马来酸酐、马来酸和富马酸中的一种或多种。
  7. 根据权利要求1所述的制备方法，其特征在于，所述链转移剂选自甲基丙烯磺酸钠、烯丙基磺酸钠、巯基乙酸、巯基丙酸、巯基乙醇、正十二烷基硫醇、次磷酸钠、乙烯基磺酸钠、丙烯基磺酸钠和苯乙烯磺酸钠中的一种或多种。
  8. 根据权利要求1所述的制备方法，其特征在于，不饱和羧酸和链转移剂通过滴加 的方法加入所述液体中，所述滴加的时间为0.5-2h。
  9. 根据权利要求1所述的制备方法，其特征在于，所述老化处理的时间为0.5-3h。
  10. 一种固体聚羧酸减水剂，其特征在于，所述固体聚羧酸减水剂是根据权利要求1至9中任一项的方法制备得到。
PCT/CN2020/090002 2020-05-13 2020-05-13 一种固体聚羧酸减水剂及其制备方法 WO2021226869A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114380529A (zh) * 2021-12-31 2022-04-22 河北圣通建材科技有限公司 一种抗泥型聚羧酸减水剂及其制备方法
CN117105596A (zh) * 2023-07-26 2023-11-24 中建三局集团有限公司 一种再生混凝土及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002201240A (ja) * 2000-12-27 2002-07-19 Nippon Shokubai Co Ltd ポリカルボン酸系共重合体の製造方法
WO2003024885A2 (en) * 2001-09-19 2003-03-27 Construction Research & Technology Gmbh Workability-improving agents for cement compositions
JP2006256887A (ja) * 2005-03-16 2006-09-28 Nof Corp セメント用添加剤
CN102741342A (zh) * 2009-09-08 2012-10-17 联合利华有限公司 支化共聚物在聚合物共混物中的用途
CN106928440A (zh) * 2015-12-29 2017-07-07 辽宁奥克化学股份有限公司 一种聚醚酰胺、由该聚醚酰胺制得的减水剂及制备方法
CN108484841A (zh) * 2018-03-30 2018-09-04 湖北工业大学 一种本体聚合的固片状聚羧酸减水剂的制备方法
CN110240676A (zh) * 2019-04-10 2019-09-17 武汉理工大学 一种固体聚羧酸减水剂的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108192041B (zh) 2017-12-29 2020-06-26 江苏苏博特新材料股份有限公司 一种粉末状聚羧酸减水剂的制备方法及应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002201240A (ja) * 2000-12-27 2002-07-19 Nippon Shokubai Co Ltd ポリカルボン酸系共重合体の製造方法
WO2003024885A2 (en) * 2001-09-19 2003-03-27 Construction Research & Technology Gmbh Workability-improving agents for cement compositions
JP2006256887A (ja) * 2005-03-16 2006-09-28 Nof Corp セメント用添加剤
CN102741342A (zh) * 2009-09-08 2012-10-17 联合利华有限公司 支化共聚物在聚合物共混物中的用途
CN106928440A (zh) * 2015-12-29 2017-07-07 辽宁奥克化学股份有限公司 一种聚醚酰胺、由该聚醚酰胺制得的减水剂及制备方法
CN108484841A (zh) * 2018-03-30 2018-09-04 湖北工业大学 一种本体聚合的固片状聚羧酸减水剂的制备方法
CN110240676A (zh) * 2019-04-10 2019-09-17 武汉理工大学 一种固体聚羧酸减水剂的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114380529A (zh) * 2021-12-31 2022-04-22 河北圣通建材科技有限公司 一种抗泥型聚羧酸减水剂及其制备方法
CN117105596A (zh) * 2023-07-26 2023-11-24 中建三局集团有限公司 一种再生混凝土及其制备方法
CN117105596B (zh) * 2023-07-26 2024-06-07 中建三局集团有限公司 一种再生混凝土及其制备方法

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