WO2015139467A1 - 一种两性甜菜碱类聚羧酸减水剂及其制备方法 - Google Patents

一种两性甜菜碱类聚羧酸减水剂及其制备方法 Download PDF

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WO2015139467A1
WO2015139467A1 PCT/CN2014/091013 CN2014091013W WO2015139467A1 WO 2015139467 A1 WO2015139467 A1 WO 2015139467A1 CN 2014091013 W CN2014091013 W CN 2014091013W WO 2015139467 A1 WO2015139467 A1 WO 2015139467A1
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monomer
reducing agent
initiator
water
betaine
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PCT/CN2014/091013
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English (en)
French (fr)
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陈少军
陈仕国
戈早川
陈程斌
古利丹
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深圳大学
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Publication of WO2015139467A1 publication Critical patent/WO2015139467A1/zh
Priority to US15/063,531 priority Critical patent/US9718733B2/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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • 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
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C08F216/1425—Monomers containing side chains of polyether groups
    • C08F216/1433—Monomers containing side chains of polyethylene oxide groups
    • 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
    • C08F220/08—Anhydrides
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/387—Esters containing sulfur and containing nitrogen and oxygen

Definitions

  • the invention relates to the technical field of concrete water reducing agents, in particular to an amphoteric betaine polycarboxylate water reducing agent and a preparation method thereof.
  • the third generation of polycarboxylate water reducers is further divided into four categories, the first being vinyl monomer copolymers and the second being propylene.
  • the base ether copolymer is an amide/polyimide type copolymer
  • the fourth type is an amphoteric vinyl polymer.
  • the amphoteric vinyl polymer water reducing agent belongs to the third generation of superplasticizers and has the best performance in the class of superplasticizers.
  • Betaine type amphoteric monomer is a kind of functional monomer which has been widely used so far, and its structure generally consists of a olefinic moiety having polymerization activity and a side group of betaine having electroneutral zwitterionic characteristics, usually having a carboxyl group.
  • These betaine-type amphoteric monomers are homopolymerized under certain conditions or copolymerized with other neutral monomers to produce an amphoteric polymer having a net charge of zero and having the behavior of an anti-polyelectrolyte solution.
  • These zwitterionic polymers are chemically and thermally stable, have a high hydration ability and contain an equal number of quaternary ammonium salt cations and sulfonate anions which are not susceptible to the pH of the solution. Get much attention.
  • the patent CN101538352A, CN102627744B, CN102443177B and the like successively disclose the preparation method of the amphoteric polymer water reducing agent.
  • These amphoteric polymers are mainly prepared by copolymerization of two monomers of cation and cation, and the process is complicated.
  • Zwitterionic polycarboxylate water reducing agents based on betaine monomers have not yet been disclosed.
  • the technical problem to be solved by the present invention is to provide an amphoteric betaine polycarboxylate water reducing agent and a preparation method thereof, so as to make up for the deficiency of the betaine type amphoteric polycarboxylate water reducing agent in the prior art.
  • the technical solution adopted by the present invention is to provide an amphoteric betaine polycarboxylate water reducing agent, wherein the amphoteric betaine polycarboxylate water reducing agent has a mass ratio of (1 to 30%): (20-50%) ): (20 to 50%) of monomer A, monomer B and monomer C are formed by aqueous solution polymerization under the action of an initiator;
  • R 1 is H or CH 3
  • R 2 is O or NH
  • R 3 is any one of CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3
  • Y is any of COO, SO 3 , PO 3 One type
  • the formula of monomer B is R 4 is H or CH 3 , and m is an average addition mole number of the oxyethylene group, and is selected from an integer of from 1 to 100;
  • the formula of monomer C is R 5 is H or CH 3 .
  • the invention also provides a preparation method of an amphoteric betaine polycarboxylate water reducing agent, comprising the following steps:
  • the temperature is raised to 60-100 ° C, and an initiator is added;
  • the reaction is kept for 4-6 hours, and after the reaction is finished, the pH is adjusted to 5-7 to obtain an aqueous solution of the amphoteric betaine polycarboxylate water reducing agent;
  • R 1 is H or CH 3
  • R 2 is O or NH
  • R 3 is any one of CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3
  • Y is any of COO, SO 3 , PO 3 One type
  • the formula of monomer B is R 4 is H or CH 3 , and m is an average addition mole number of the oxyethylene group, and is selected from an integer of from 1 to 100;
  • the formula of monomer C is R 5 is H or CH 3 .
  • the preparation method of the amphoteric betaine polycarboxylate water reducing agent of the invention has simple reaction process and is environmentally friendly and non-polluting; the polyglycolic acid water reducing agent prepared by the betaine has an amphoteric structure and has strong dispersion effect on concrete; the reaction system has no Cl ion It has no corrosive effect on building materials; it can be widely used in high performance concrete, recycled concrete, moisturizing concrete, ceramic products, brick and tile products to improve fluidity, reduce water consumption and reduce energy consumption.
  • the present invention provides an amphoteric betaine polycarboxylate water reducing agent, wherein the amphoteric betaine polycarboxylate water reducing agent has a mass ratio of (1-30%): (20-50%): (20 ⁇ 50%) of monomer A, monomer B and monomer C are formed by aqueous solution polymerization under the action of an initiator;
  • R 1 is H or CH 3
  • R 2 is O or NH
  • R 3 is any one of CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3
  • Y is any of COO, SO 3 , PO 3 One type
  • the formula of monomer B is R 4 is H or CH 3 , and m is an average addition mole number of the oxyethylene group, and is selected from an integer of from 1 to 100;
  • the formula of monomer C is R 5 is H or CH 3 .
  • the embodiment of the invention further provides a preparation method of an amphoteric betaine polycarboxylate water reducing agent, comprising the following steps:
  • R 1 is H or CH 3
  • R 2 is O or NH
  • R 3 is any one of CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3
  • Y is any of COO, SO 3 , PO 3 One type
  • the formula of monomer B is R 4 is H or CH 3 , and m is an average addition mole number of the oxyethylene group, and is selected from an integer of from 1 to 100;
  • the formula of monomer C is R 5 is H or CH 3 .
  • Step (1) adding water and stirring, preferably adding deionized water, stirring uniformly, and then adding monomer C as described in step (2) after mixing, the mass fraction of the three monomers is 1 to 30%, 20 to 50, respectively. %, 20 to 50%. After the three monomers are uniformly mixed, deionized water is added to adjust so that the total mass of the three monomers accounts for 10-20% of the total mass of the aqueous solution.
  • the initiator aqueous solution is heated to 60 to 100 ° C while stirring under an inert gas (for example, nitrogen).
  • the initiator is a free radical water-soluble initiator, preferably ammonium persulfate, potassium persulfate or redox initiator, the initiator is used in an amount of 0.5 to 2% of the total mass of the monomer; when the initiator is added, the batch should be divided into batches. It is slowly added, preferably divided into three batches, and a total of 1/3 of the initiator is added dropwise per hour.
  • Step (4) after the completion of the initiator addition, the temperature is kept for 4-6 hours, and after the reaction is completed, it is cooled to room temperature, and the pH of the solution is adjusted to 5-7 at room temperature, preferably 1-3 mol/ The alkaline aqueous solution of NaOH of L is adjusted, and further preferably 3 mol/L. The mass fraction of the aqueous solution of the prepared water reducing agent is adjusted to be 10 to 30%.
  • the preparation method of the amphoteric betaine polycarboxylate water reducing agent of the invention has simple reaction process and is environmentally friendly and non-polluting; the polyglycolic acid water reducing agent prepared by the betaine has an amphoteric structure and has strong dispersion effect on concrete; the reaction system has no Cl ion It has no corrosive effect on building materials; the performance of water reducing agent is stable, the water reducing rate is high, the cement has strong adaptability and the compounding effect is good. It can be widely used in high performance concrete, recycled concrete, moisturizing concrete, ceramic products, brick products. Improve fluidity during preparation, reduce water use, and reduce energy consumption.
  • the aqueous solution was cooled to room temperature, the pH was adjusted to 6-7 with a 3 mol/L NaOH solution, and the solid content of the aqueous solution was adjusted to 25% to obtain a betaine polyglycol of the MPEG-DMHAS-MA-2 system.
  • a carboxylic acid water reducing agent According to the test method of the national standard GB 8077-2000, the fluidity of the cement paste of the water reducing agent is 245 mm.
  • TPEG 1000 allyl polyoxyethylene ether
  • DPAS N,N-dimethyl(methacryloyloxyethyl)ammonium propanesulfonic acid inner salt
  • allyl polyoxyethylene ether TPEG3000 having a molecular weight of 3000
  • 8 g of N,N-dimethyl(methacryloyloxyethyl)ammonium propanesulfonic acid inner salt DPAS
  • AA acrylic acid
  • 0.09 g of ammonium persulfate was added for the first time, and after reacting for 1 hour, 0.09 g of ammonium persulfate was further added.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明公开了一种两性甜菜碱类聚羧酸减水剂及其制备方法。将不饱和甜菜碱类单体A和丙烯酸类聚乙二醇单体B置于反应容器中，搅拌均匀后再加入丙烯酸类单体C，继续搅拌并加水调节使单体的总质量占水溶液总质量的10％～20％；在惰性气体保护下，升温至60～100℃，加入引发剂水溶液保温反应4～6h，待反应结束后冷却到室温调节溶液的pH值至5～7制得两性甜菜碱类聚羧酸减水剂。本发明所制备的聚羧酸减水剂性能稳定，减水率高，水泥适应性强，复配效果好，对环境无污染，能广泛应用于高性能混凝土，再生混凝土，保湿混凝土，陶瓷产品，砖瓦产品的制备中提高流动性，减少用水，降低能耗。

Description

一种两性甜菜碱类聚羧酸减水剂及其制备方法 技术领域
本发明涉及混凝土减水剂技术领域，尤其涉及一种两性甜菜碱类聚羧酸减水剂及其制备方法。
背景技术
随着建筑工业和科学技术的不断发展，混凝土用途越来越广，对混凝土技术性能要求也越来越高。实践证明，应用外加剂是混凝土技术进步的主要途径，它能使混凝土满足各种不同的施工要求，具有投资少，见效快，推广应用较容易，技术经济效益显著等特点。减水剂就是最重要的混凝土外加剂之一。
近年来，混凝土减水剂的研究与生产已经朝着高性能、无污染方向发展。如美国、日本、意大利等国已在水利、道路等要求高耐久的混凝土工程中广泛应用到马来酸酐系、丙烯酸系高性能混凝土减水剂，技术虽然比较成熟，但存在着工艺复杂、反应要求高等问题，不利于推广。
高效减水剂的研究发展到第三代聚羧酸减水剂，而第三代聚羧酸减水剂又分为四类，第一类是乙烯基单体共聚物，第二类是丙烯基醚共聚物，第三类是酰胺/聚酰亚胺型共聚物，第四类为两性乙烯基聚合物。两性乙烯基聚合物减水剂属于第三代高效减水剂中性能效果最好的一类高效减水剂。
甜菜碱型两性单体是迄今应用十分广泛的一类功能性单体，其结构一般由具有聚合活性的烯键部分和具有电中性两性离子化特征的甜菜碱侧基部分组成，通常有羧酸甜菜碱型和磺酸甜菜碱型两种。这些甜菜碱型两性单体在一定条件下均聚或与其它中性单体共聚可制得净电荷为零的、具有反聚电解质溶液行为的两性聚合物。这些两性离子聚合物因其化学性和热稳定性好、水化能力强且含有不易受溶液pH值影响的等数目的季铵盐阳离子和磺酸盐阴离子而 倍受关注。
专利CN101538352A，CN102627744B，CN102443177B等先后公开了两性聚合物减水剂的制备方法，这些两性聚合物主要通过阳、阳离子两种单体共聚制备，工艺复杂。目前还没有公开基于甜菜碱单体的两性离子聚羧酸减水剂。
发明内容
本发明所要解决的技术问题在于提供一种两性甜菜碱类聚羧酸减水剂及其制备方法，以弥补现有技术中尚没有甜菜碱型两性聚羧酸减水剂的不足。
本发明所采用的技术方案是提供一种两性甜菜碱类聚羧酸减水剂，所述两性甜菜碱类聚羧酸减水剂由质量比为(1～30％)：(20～50％)：(20～50％)的单体A、单体B和单体C在引发剂的作用下进行水溶液聚合而成；
其中，单体A的通式为
Figure PCTCN2014091013-appb-000001
R1为H或者CH3，R2为O或者NH，R3为CH3,CH2CH3，CH2CH2CH3中的任意一种，Y为COO,SO3,PO3中的任意一种；
单体B的通式为
Figure PCTCN2014091013-appb-000002
R4为H或者CH3，m为氧化乙烯基的平均加成摩尔数，选自1～100的整数；
单体C的通式为
Figure PCTCN2014091013-appb-000003
R5为H或者CH3。
本发明还提供一种两性甜菜碱类聚羧酸减水剂的制备方法，包括以下步骤：
将单体A和单体B置于反应容器中，加水搅拌；
在所述反应容器中再加入单体C，搅拌并加水调节使单体的总质量占水溶液总质量的10～20％；单体A、单体B和单体C的质量比为(1～30％)：(20～50％)：(20～50％)；
在惰性气体保护下，升温至60～100℃，加入引发剂；
保温反应4～6h，反应结束后，调节pH值至5～7，获得两性甜菜碱类聚羧酸减水剂水溶液；
其中，单体A的通式为
Figure PCTCN2014091013-appb-000004
R1为H或者CH3，R2为O或者NH，R3为CH3,CH2CH3,CH2CH2CH3中的任意一种，Y为COO,SO3,PO3中的任意一种；
单体B的通式为
Figure PCTCN2014091013-appb-000005
R4为H或者CH3，m为氧化乙烯基的平均加成摩尔数，选自1～100的整数；
单体C的通式为
Figure PCTCN2014091013-appb-000006
R5为H或者CH3。
本发明两性甜菜碱类聚羧酸减水剂制备方法反应工艺简单，且环保无污染；所制得甜菜碱类聚羧酸减水剂具有两性结构，对混凝土分散作用强；反应体系没有Cl离子，对建筑材料无腐蚀作用；能广泛应用于高性能混凝土，再生混凝土，保湿混凝土，陶瓷产品，砖瓦产品的制备中提高流动性，减少用水，降低能耗。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，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。
本发明实施例提供一种两性甜菜碱类聚羧酸减水剂，所述两性甜菜碱类聚羧酸减水剂由质量比为(1～30％)：(20～50％)：(20～50％)的单体A、单体B和单体C在引发剂的作用下进行水溶液聚合而成；
其中，单体A的通式为
Figure PCTCN2014091013-appb-000007
R1为H或者CH3，R2为O或者NH，R3为CH3,CH2CH3，CH2CH2CH3中的任意一种，Y为COO,SO3,PO3中的任意一种；
单体B的通式为
Figure PCTCN2014091013-appb-000008
R4为H或者CH3，m为氧化乙烯基的平均加成摩尔数，选自1～100的整数；
单体C的通式为
Figure PCTCN2014091013-appb-000009
R5为H或者CH3。
本发明实施例还提供一种两性甜菜碱类聚羧酸减水剂的制备方法，包括以下步骤：
(1)将单体A和单体B置于反应容器中，加水搅拌；
(2)在所述反应容器中再加入单体C，搅拌并加水调节使单体的总质量占水溶液总质量的10～20％；单体A、单体B和单体C的质量比为(1～30％)：(20～50％)：(20～50％)；
(3)在惰性气体保护下，升温至60～100℃，加入引发剂；
(4)保温反应4～6h，反应结束后，调节pH值至5～7，获得两性甜菜碱类聚羧酸减水剂水溶液；
其中，单体A的通式为
Figure PCTCN2014091013-appb-000010
R1为H或者CH3，R2为O或者NH，R3为CH3,CH2CH3,CH2CH2CH3中的任意一种，Y为COO,SO3,PO3中的任意一种；
单体B的通式为
Figure PCTCN2014091013-appb-000011
R4为H或者CH3，m为氧化乙烯基的平均加成摩尔数，选自1～100的整数；
单体C的通式为
Figure PCTCN2014091013-appb-000012
R5为H或者CH3。
步骤(1)，加水搅拌优选加入去离子水后搅拌均匀，混匀后再如步骤(2)所述加入单体C，三种单体的质量分数依次分别为1～30％、20～50％、20～50％。三种单体混合均匀后再加入去离子水调节使得三种单体的总质量占水溶液总质量的10～20％。
步骤(3)，需在惰性气体(如氮气)保护下边搅拌边升温至60～100oC加入引发剂水溶液。其中，引发剂为自由基水溶性引发剂，优选过硫酸铵、过硫酸钾或氧化还原引发剂，引发剂的使用量为单体总质量的0.5～2％；加入引发剂时应分批次缓慢加入，优选分为三个批次，每个小时滴入1/3总量的引发剂。
步骤(4)，引发剂加入完成后需维持温度保温反应4～6个小时，待反应完全后冷却至室温，在室温条件下，调节溶液的pH值到5～7，优选加入1～3mol/L的NaOH碱性水溶液进行调节，进一步为优选3mol/L。调节使得所制备减水剂水溶液的质量分数为10～30％。
本发明两性甜菜碱类聚羧酸减水剂制备方法反应工艺简单，且环保无污染；所制得甜菜碱类聚羧酸减水剂具有两性结构，对混凝土分散作用强；反应体系没有Cl离子，对建筑材料无腐蚀作用；减水剂性能稳定，减水率高，水泥适应性强，复配效果好，能广泛应用于高性能混凝土，再生混凝土，保湿混凝土，陶瓷产品，砖瓦产品的制备中提高流动性，减少用水，降低能耗。
实施例1
将10g分子量为1000的甲基烯丙基聚氧乙烯醚(MPEG1000)、2g N，N-二甲基(甲基丙烯酰氧乙基)铵基丙磺酸内盐(DMPAS)投入到盛有100g蒸馏水的反应容器中，加热搅拌均匀后，再加入5g丙烯酸(AA)，边搅拌边升温水浴温度至75℃时，第一次加入0.05g过硫酸铵，反应1h后，再加入0.05g过硫酸铵；再反应1h后，最后再加入0.05g过硫酸铵。保温反应4小时后，将水溶液冷却至室温，采用3mol/L的NaOH溶液调节使pH值为6～7，且水溶液固含量为20％，即可得到MPEG-DMPAS-AA-1体系的甜菜碱类聚羧酸减水剂。参照国标GB 8077—2000的试验方法测试，此减水剂的水泥净浆流动度为265mm。
实施例2
将10g分子量为2000的甲基烯丙基聚氧乙烯醚(MPEG2000)、4g N,N-二甲基-N-甲基丙烯酰胺基丙基-N-丙烷磺酸内盐(DMHAS)投入到盛有100g蒸馏水的反应容器中，加热搅拌均匀后，再加入5g甲基丙烯酸(MA)，边搅拌边升温水浴温度至75℃时，第一次加入0.06g过硫酸铵，反应1h后，再加入0.06g过硫酸铵；再反应1h后，最后再加入0.06g过硫酸铵。保温反应4小时后，将水溶液冷却至室温，采用3mol/L的NaOH溶液调节pH为6～7，调节水溶液固含量为25％，即可得到MPEG-DMHAS-MA-2体系的甜菜碱类聚羧酸减水剂。参照国标GB 8077—2000的试验方法测试，此减水剂的水泥净浆流动度为245mm。
实施例3
将10g分子量为1000的烯丙基聚氧乙烯醚(TPEG1000)、4g N,N-二甲基(甲基丙烯酰氧乙基)铵基丙磺酸内盐(DMPAS)投入到盛有100g蒸馏水的反应容器中，加热搅拌均匀后，再加入5g甲基丙烯酸(MA)，边搅拌边升温 水浴温度至75℃时，第一次加入0.07g过硫酸铵，反应1h后，再加入0.07g过硫酸铵；再反应1h后，最后再加入0.07g过硫酸铵。保温反应4小时后，将水溶液冷却至室温，采用3mol/L的NaOH溶液调节pH为6～7，调节水溶液固含量为15％，即可得到TPEG-DMPAS-MA-3体系的甜菜碱类聚羧酸减水剂。参照国标GB 8077—2000的试验方法测试，此减水剂的水泥净浆流动度为295mm。
实施例4
将10g分子量为2000的烯丙基聚氧乙烯醚(TPEG2000)、6g N,N-二甲基-N-甲基丙烯酰胺基丙基-N-丙烷磺酸内盐(DMHAS)投入到盛有100g蒸馏水的反应容器中，加热搅拌均匀后，再加入5g甲基丙烯酸(MA)，边搅拌边升温水浴温度至75℃时，第一次加入0.08g过硫酸铵，反应1h后，再加入0.08g过硫酸铵；再反应1h后，最后再加入0.08g过硫酸铵。保温反应4小时后，将水溶液冷却至室温，采用3mol/L的NaOH溶液调节pH为6～7,调节水溶液固含量为30％，即可得到TPEG-DMHAS-MA-4体系的甜菜碱类聚羧酸减水剂。参照国标GB 8077—2000的试验方法测试，此减水剂的水泥净浆流动度为305mm。
实施例5
将10g分子量为3000的烯丙基聚氧乙烯醚(TPEG3000)、8g N，N-二甲基(甲基丙烯酰氧乙基)铵基丙磺酸内盐(DMPAS)投入到盛有100g蒸馏水的反应容器中，加热搅拌均匀后，再加入5g丙烯酸(AA)，边搅拌边升温水浴温度至75℃时，第一次加入0.09g过硫酸铵，反应1h后，再加入0.09g过硫酸铵；再反应1h后，最后再加入0.09g过硫酸铵。保温反应4小时后，将水溶液冷却至室温，采用3mol/L的NaOH溶液调节pH为6～7，调节水溶液固含量为20％，即可得到TPEG-DMPAS-AA-5体系的甜菜碱类聚羧酸减水剂。 参照国标GB8077—2000的试验方法测试，此减水剂的水泥净浆流动度为270mm。
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。

Claims (7)

  1. 一种两性甜菜碱类聚羧酸减水剂，其特征在于，所述两性甜菜碱类聚羧酸减水剂由质量比为(1～30％)：(20～50％)：(20～50％)的单体A、单体B和单体C在引发剂的作用下进行水溶液聚合而成；
    其中，单体A的通式为
    Figure PCTCN2014091013-appb-100001
    R1为H或者CH3，R2为O或者NH，R3为CH3,CH2CH3，CH2CH2CH3中的任意一种，Y为COO,SO3,PO3中的任意一种；
    单体B的通式为
    Figure PCTCN2014091013-appb-100002
    R4为H或者CH3，m为氧化乙烯基的平均加成摩尔数，选自1～100的整数；
    单体C的通式为
    Figure PCTCN2014091013-appb-100003
    R5为H或者CH3。
  2. 一种两性甜菜碱类聚羧酸减水剂的制备方法，其特征在于，包括以下步骤：
    将单体A和单体B置于反应容器中，加水搅拌；
    在所述反应容器中再加入单体C，搅拌并加水调节使单体的总质量占水溶液总质量的10～20％；单体A、单体B和单体C的质量比为(1～30％)：(20～50％)：(20～50％)；
    在惰性气体保护下，升温至60～100℃，加入引发剂；
    保温反应4～6h，反应结束后，调节pH值至5～7，获得所述两性甜菜碱类聚羧酸减水剂水溶液；
    其中，单体A的通式为
    Figure PCTCN2014091013-appb-100004
    R1为H或者CH3，R2为O或者NH，R3为CH3,CH2CH3,CH2CH2CH3中的任意一种，Y为COO,SO3,PO3中的任意一种；
    单体B的通式为
    Figure PCTCN2014091013-appb-100005
    R4为H或者CH3，m为氧化乙烯基的平均加成摩尔数，选自1～100的整数；
    单体C的通式为
    Figure PCTCN2014091013-appb-100006
    R5为H或者CH3。
  3. 根据权利要求2所述的两性甜菜碱类聚羧酸减水剂的制备方法，其特征在于，所述引发剂为自由基水溶性引发剂，所述引发剂总质量占单体总质量的0.5～2.0％。
  4. 根据权利要求2或3所述的两性甜菜碱类聚羧酸减水剂的制备方法，其特征在于，所述引发剂为过硫酸铵、过硫酸钾或氧化还原引发剂中的至少一种。
  5. 根据权利要求2所述的两性甜菜碱类聚羧酸减水剂的制备方法，其特征在于，所述引发剂在加入之前配制成水溶液；所述加入引发剂的方法是每小时滴入1/3总量的引发剂水溶液。
  6. 根据权利要求2所述的两性甜菜碱类聚羧酸减水剂的制备方法，其特征在于，所述调节pH值至5～7的方法是加入1～3mol/L的NaOH碱性水溶液进行调节。
  7. 根据权利要求2所述的两性甜菜碱类聚羧酸减水剂的制备方法，其特征在于，所述水为去离子水。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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* Cited by examiner, † Cited by third party
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CN112408848B (zh) * 2020-11-25 2022-05-13 山西桑穆斯建材化工有限公司 一种聚羧酸高性能减水剂的制备方法
CN113563541B (zh) * 2021-09-23 2021-12-14 山东同盛建材有限公司 一种聚羧酸减水剂的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101538352A (zh) * 2009-04-10 2009-09-23 陕西科技大学 一种两性乙烯基类聚合物减水剂的制备方法
CN102617065A (zh) * 2012-03-06 2012-08-01 上海市建筑科学研究院(集团)有限公司 一种具有保坍性能的多支链聚羧酸减水剂及其制备方法
CN103253886A (zh) * 2013-04-12 2013-08-21 奥克化学扬州有限公司 一种聚羧酸减水剂增效剂及其制备方法
CN103923275A (zh) * 2014-03-18 2014-07-16 深圳大学 一种两性甜菜碱类聚羧酸减水剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102453194B (zh) * 2010-10-25 2014-07-09 中国石油化工股份有限公司 一种共聚物及其制备方法
CN102351999A (zh) * 2011-07-15 2012-02-15 清华大学 一种纳米粒子型减水剂的制备方法
CN102443177B (zh) 2011-11-01 2013-03-20 陕西科技大学 一种两性壳聚糖减水剂的制备方法
CN102627744B (zh) 2012-04-11 2013-06-19 长沙加美乐素化工有限公司 一种醚类两性聚羧酸减水剂的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101538352A (zh) * 2009-04-10 2009-09-23 陕西科技大学 一种两性乙烯基类聚合物减水剂的制备方法
CN102617065A (zh) * 2012-03-06 2012-08-01 上海市建筑科学研究院(集团)有限公司 一种具有保坍性能的多支链聚羧酸减水剂及其制备方法
CN103253886A (zh) * 2013-04-12 2013-08-21 奥克化学扬州有限公司 一种聚羧酸减水剂增效剂及其制备方法
CN103923275A (zh) * 2014-03-18 2014-07-16 深圳大学 一种两性甜菜碱类聚羧酸减水剂及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112500534A (zh) * 2020-12-03 2021-03-16 贵州石博士科技股份有限公司 一种两性型聚羧酸减水剂及其制备方法

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