WO2022116596A1 - 一种混凝土微沫剂及其制备方法 - Google Patents

一种混凝土微沫剂及其制备方法 Download PDF

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Publication number
WO2022116596A1
WO2022116596A1 PCT/CN2021/112824 CN2021112824W WO2022116596A1 WO 2022116596 A1 WO2022116596 A1 WO 2022116596A1 CN 2021112824 W CN2021112824 W CN 2021112824W WO 2022116596 A1 WO2022116596 A1 WO 2022116596A1
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agent
concrete
parts
microfoaming
water
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PCT/CN2021/112824
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English (en)
French (fr)
Inventor
曾贤华
徐逸丹凤
朱巧勇
黄文耀
沈聪聪
于飞宇
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科之杰新材料集团浙江有限公司
科之杰新材料集团有限公司
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Publication of WO2022116596A1 publication Critical patent/WO2022116596A1/zh

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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
    • C04B24/16—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to the technical field of concrete admixtures, in particular to a concrete microfoaming agent and a preparation method thereof.
  • concrete microfoaming agent can greatly improve the workability of concrete and greatly improve the durability of concrete.
  • the commonly used concrete microfoaming agents on the market are anionic surfactants, which have surface-active effects such as air-entraining, dispersing, and wetting.
  • air-entraining effects are the main ones, and most of them belong to the category of rosin-type air-entraining agents.
  • Commonly used anionic surfactants with rosin sodium salt as the main body however, the concrete microfoaming agent of this type of anionic surfactants has the problems of poor stability, poor workability and too sensitive to storage and stirring time in use. Therefore, the invention of a concrete microfoaming agent with good stability, good workability and insensitivity to storage and mixing time is of great significance for improving the performance of concrete.
  • the present invention provides a kind of concrete micro-foaming agent, in parts by weight, the concrete micro-foaming agent comprises:
  • Sulfonating agent 100 ⁇ 150 parts
  • Alkali agent 0 ⁇ 100 parts
  • Extender 200 ⁇ 400 copies
  • the sulfonating agent includes one or more of sulfite, metabisulfite and bisulfite.
  • the sulfonating agent includes one or more of sodium sulfite, sodium metabisulfite and sodium bisulfite.
  • the unilateral condensing agent includes one or more of butanone and butanone derivatives.
  • the butanone derivatives include one or more of methyl isobutyl ketone, 3-hydroxybutanone and 3-mercapto-2-butanone.
  • the linking agent includes one or more of formaldehyde and acetaldehyde.
  • the concentration of formaldehyde is 37%.
  • the alkali agent is one or more of sodium hydroxide and potassium hydroxide.
  • the present invention also provides a preparation method of concrete microfoaming agent, comprising the following steps:
  • step (1) control the temperature of step (1) to rise to 60 ⁇ 70°C, add 100 ⁇ 200 parts of unilateral condensing agent and 200 ⁇ 400 parts of linking agent to the dissolved solution, and control the temperature at 95 ⁇ 100°C After the heat preservation is completed, 50 to 200 parts of water are added to obtain the concrete microfoaming agent.
  • step (1) fully stir for 10-30 min at 50-65° C. until the sulfonating agent and the alkali agent are completely dissolved in water to obtain a dissolved solution.
  • the concrete micro-foaming agent provided in the embodiment of the present invention uses a unilateral condensing agent and other components to carry out a unilateral condensation reaction to obtain a concrete micro-foaming agent of a class of small-molecule polymers.
  • the concrete microfoaming agent in the present invention has good bubble stability, is less affected by concrete mixing time and storage time, greatly improves the workability, fluidity and construction performance of concrete, and has a higher water reduction rate. and value for money.
  • the experimental methods in the following examples are conventional methods unless otherwise specified.
  • the test materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.
  • the quantitative experiments in the following examples are all set up three repeated experiments, and the data are the mean value or the mean ⁇ standard deviation of the three repeated experiments.
  • Embodiments of the present invention provide a concrete micro-foaming agent, in parts by weight, the concrete micro-foaming agent comprises:
  • Sulfonating agent 100 ⁇ 150 parts
  • Alkali agent 0 ⁇ 100 parts
  • Extender 200 ⁇ 400 copies
  • the concrete micro-foaming agent provided in the embodiment of the present invention uses a unilateral condensing agent and other components to carry out a unilateral condensation reaction to obtain a concrete micro-foaming agent of a class of small-molecule polymers.
  • the concrete microfoaming agent in the present invention has good bubble stability, is less affected by concrete mixing time and storage time, greatly improves the workability, fluidity and construction performance of concrete, and has a higher water reduction rate. and value for money.
  • the sulfonating agent includes one or more of sulfite, metabisulfite and hydrogen sulfite, and the sulfonic acid group after the above-mentioned sulfonating agent is dissolved in water is hydrolyzed in an aqueous solution , so that the concrete microfoam reaction system is alkaline, so as to promote the condensation reaction of each component in the concrete microfoam reaction system to obtain a small molecular polymer concrete microfoam.
  • the above-mentioned sulfonated agent can also A sulfonation reaction occurs with the unilateral condensing agent and the linking agent in the concrete microfoaming agent reaction system to provide hydroxyl and sulfonic acid groups, thereby promoting the condensation reaction.
  • the sulfonating agent includes one or more of sodium sulfite, sodium metabisulfite and sodium hydrogen sulfite, so as to more effectively promote the condensation reaction.
  • the purity of sodium sulfite is greater than or equal to 96%, so as to effectively improve the reaction efficiency in the concrete microfoaming agent reaction system.
  • the purity of sodium metabisulfite is greater than or equal to 96%, so as to effectively improve the reaction efficiency in the concrete microfoaming agent reaction system.
  • the purity of sodium bisulfite is greater than or equal to 96%, so as to effectively improve the reaction efficiency in the concrete microfoaming agent reaction system.
  • the unilateral condensing agent includes butanone or butanone derivatives, butanone or butanone derivatives, and primary carbons on both sides of the carbonyl group of butanone or butanone derivatives, That is, there are three hydrogens on the carbon, and the other side is not a primary carbon, which makes the condensation reaction of butanone or butanone derivatives a unilateral condensation reaction, so that the obtained concrete microfoaming agent is a small-molecule polymer concrete Microfoam.
  • the butanone derivatives include one or more of methyl isobutyl ketone, 3-hydroxybutanone and 3-mercapto-2-butanone.
  • the linking agent includes one or more of formaldehyde and acetaldehyde, so as to effectively adjust the molecular weight of the concrete micro-foaming agent to obtain the small-molecule polymer-based concrete micro-foaming agent of the present invention.
  • the concentration of formaldehyde is 37% to more effectively adjust the molecular weight of the concrete microfoaming agent, and the formaldehyde concentration of 37% is suitable for other components in the concrete microfoaming agent reaction system to obtain
  • concentration of various concrete microfoaming agents with superior performance ensures that formaldehyde will not be used excessively and cause environmental pollution.
  • the concentration of acetaldehyde is 40% to more effectively adjust the molecular weight of the concrete microfoam, and the acetaldehyde concentration of 40% is compatible with other components in the concrete microfoam reaction system In order to obtain the concentration of concrete microfoaming agent with superior performance, it can ensure that acetaldehyde will not be used excessively and achieve the effect of energy saving.
  • the alkali agent is one or more of sodium hydroxide and potassium hydroxide, and the hydrolysis of the sulfonic acid group in the sulfonating agent in water cannot make the concrete microfoaming agent reaction system achieve the required reaction Under the condition of alkaline environment, the alkaline agent is supplemented to adjust the pH of the concrete microfoaming agent reaction system to 9.0-11.0, so as to achieve the alkaline environment required for the reaction.
  • the alkali agent includes one or more of sodium hydroxide with a concentration of 50% and potassium hydroxide with a concentration of 50%, so as to effectively adjust the pH in the reaction system of the concrete microfoaming agent to 9.0-11.0, to avoid The pH in the concrete microfoam reaction system is not suitable for the pH required for the reaction.
  • the present invention also provides a method for preparing a concrete microfoaming agent, comprising the following steps:
  • step (1) control the temperature of step (1) to rise to 60 ⁇ 70°C, add 100 ⁇ 200 parts of unilateral condensing agent and 200 ⁇ 400 parts of linking agent to the dissolved solution, and control the temperature at 95 ⁇ 100°C After the heat preservation is completed, 50 to 200 parts of water are added to obtain the concrete microfoaming agent.
  • the embodiment of the present invention provides a preparation method of a concrete microfoaming agent.
  • a sulfonating agent is added to the concrete microfoaming agent reaction system, and the pH is adjusted to 9.0-11.0 by an alkali agent, and then the Stir thoroughly at 65°C until the sulfonating agent and the alkali agent are completely dissolved in the water, and a dissolved solution is obtained, so that the concrete microfoam reaction system is in an alkaline environment, so as to promote the subsequent unilateral condensation in the concrete microfoam reaction system.
  • the reaction is carried out, and the sulfonic acid group generated by the sulfonating agent dissolved in water undergoes a sulfonation reaction with the unilateral condensing agent and the extender in the concrete microfoaming agent reaction system to provide hydroxyl groups and sulfonic acid groups, which can also be used. Promote the subsequent unilateral condensation reaction; at the same time, under the alkaline environment and the above conditions, the unilateral condensation reaction of the unilateral condensing agent and the linking agent in the dissolved solution occurs, and 50 to 200 parts of water are added.
  • the concrete in the present invention to adjust the concrete micro-foaming agent after the unilateral condensation reaction is completed to the desired ideal concentration, that is, to obtain a concrete micro-foaming agent of a small molecular polymer class, and the concentration is the ideal concentration required for construction, the concrete in the present invention
  • the microfoaming agent has the advantages of good bubble stability and little influence by the concrete mixing time and storage time, and the concrete microfoaming agent in the present invention can greatly improve the workability, fluidity and construction performance of concrete, and has higher performance. Water reduction and cost performance.
  • step (1) fully stir for 10-30 min at 50-65° C. until the sulfonating agent and the alkali agent are completely dissolved in water to obtain a dissolved solution, so that the sulfonating agent and the alkali are completely dissolved.
  • the agent is fully dissolved, increasing the stability of the dissolved solution.
  • step (2) after the heat preservation is completed, the temperature is lowered to 70-75° C., and 50-200 parts of water are added to obtain a concrete microfoaming agent.
  • control step (1) rises to 65 °C, adds 150 parts of butanone, 300 parts of formaldehyde in the solution after dissolving, and controls the reaction temperature to be 96 °C, insulation 4.0h, after insulation finishes, cooling When the temperature is below 70°C, 100 parts of water are added to obtain concrete microfoaming agent.
  • control step (1) rises to 65 °C, adds 160 parts of 3-hydroxybutanone, 300 parts of formaldehyde in the solution after dissolving, and controls the reaction temperature to be 96 °C, insulation 4.0h, insulation finishes After that, the temperature is lowered to below 70°C, and 50 parts of water are added to obtain the concrete microfoaming agent.
  • control step (1) rises to 68 °C, adds 180 parts of 3-mercapto-2-butanone, 350 parts of acetaldehyde in the solution after dissolving, and controls the reaction temperature to be 96 °C, heat preservation 5.0 h, after the heat preservation is completed, the temperature is lowered to below 70°C, and 120 parts of water are added to obtain the concrete microfoaming agent.
  • control step (1) rises to 68 °C, in the solution after dissolving, add 100 parts of butanone and 60 parts of 3-hydroxybutanone, 300 parts of formaldehyde, and control the reaction temperature to be 96 °C, Heat preservation for 4.0h, after the heat preservation is completed, the temperature is lowered to below 70°C, and 100 parts of water are added to obtain the concrete microfoaming agent.
  • Example 1-4 the concrete micro-foaming agent obtained in Example 1-4 and the commercially available traditional concrete micro-foaming agent are added to the concrete of each group, and the concrete micro-foaming agent and the commercially available traditional concrete micro-foaming agent in Example 1-4 will be added.
  • the concrete of each group is stored and stirred for 60min, wherein, in parts by weight, the concrete mix ratios of each group are as shown in Table 1, the concrete of each group is the same concrete, and the cement adopts the southern P.O42.5R cement, coal
  • the ash is grade II coal ash
  • the mineral powder is S95 mineral powder
  • the fine sand is the fine sand with a fineness modulus of 1.2
  • the machine-made sand is the machine-made sand with a fineness modulus of 3.0
  • the crushed stone is with a particle size of 5-25.
  • the superplasticizer is PCE polycarboxylate superplasticizer, wherein the content of PCE polycarboxylate superplasticizer includes cement, coal ash, mineral powder, fine sand, machine-made sand, crushed stone and 2.0% of the total mass of the glue material including water (converted to 0.20% as solid), the concrete microfoaming agent obtained in Examples 1-4 and the commercially available traditional concrete microfoaming agent are all PCE polycarboxylate water reducing agents. 0.1% of the dosage of the agent.
  • GB8076-2008 Concrete Admixtures
  • GBT 50081-2002 Experimental Methods for Mechanical Properties of Ordinary Concrete
  • the concrete micro-foaming agent in Examples 1-4 of the present invention is compared with the commercially available traditional concrete micro-foaming agent in Comparative Example 1, the concrete micro-foaming agent in the present invention. It has higher concrete water reduction rate and better workability; secondly, the gas content of the sample in Comparative Example 1 changed from 1.0% to 0.2% within 0min to 60min.
  • Example 1- The air content of the samples in 4 is not obvious within 0min to 60min, and the change trend is not obvious. It can be seen from the above that the concrete microfoaming agent in the present invention has a higher air content, and has good bubble stability.
  • the compressive strength of the samples in Examples 1-4 of the present invention and the sample in Comparative Example 1 are increased within 7d to 28d, and both have superior compressive strength, which can illustrate the present invention
  • the medium concrete microfoaming agent has no obvious effect on the compressive strength of concrete at different ages, and can make the concrete have superior strength. Therefore, the concrete added with the medium concrete microfoaming agent of the present invention has the advantage of high strength.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

本发明涉及一种混凝土微沫剂，以重量份数计，混凝土微沫剂包括：磺化剂：100～150份；碱剂：0～100份；单边缩合剂：100～200份；扩联剂：200～400份；水：250～600份，本发明以单边缩合剂及其他组分进行单边缩合反应，以得到一类小分子聚合物的混凝土微沫剂，此外，本发明中的混凝土微沫剂具有气泡稳定性好、受混凝土搅拌时间和存放时间的影响小，且极大改善了混凝土的和易性、流动性和施工性能，具有更高的减水率和性价比。

Description

一种混凝土微沫剂及其制备方法 技术领域
本发明涉及混凝土外加剂技术领域，具体为一种混凝土微沫剂及其制备方法。
背景技术
混凝土外加剂在改善混凝土性能方面的技术优势逐渐突出，混凝土微沫剂作为混凝土外加剂的一种，其可以大幅改善混凝土和易性，并且能够大大提高混凝土的耐久性。
目前，市场上常用的混凝土微沫剂为阴离子表面活性剂，具有引气、分散、润湿等表面活性作用，其中以引气作用为主，多属于松香类引气剂的范畴。常见的为以松香钠盐为主体的阴离子表面活性剂，然而这一类阴离子表面活性剂的混凝土微沫剂在使用中存在稳定性差，和易性差及对存放和搅拌时间过于敏感的问题。因此，发明一种稳定性好、和易性好及对存放和搅拌时间不敏感的混凝土微沫剂对改善混凝土性能有着重要意义。
发明内容
基于此，有必要提供一种混凝土微沫剂及其制备方法，以实现混凝土微沫剂具有稳定性好、和易性好及对搅拌时间不敏感的优点。
为实现上述目的，本发明提供一种混凝土微沫剂，以重量份数计，混凝土微沫剂包括：
磺化剂：100～150份；
碱剂：0～100份；
单边缩合剂：100～200份；
扩联剂：200～400份；
水：250～600份。
优选地，磺化剂包括亚硫酸盐、焦亚硫酸盐和亚硫酸氢盐中的一种或多 种。
优选地，磺化剂包括亚硫酸钠、焦亚硫酸钠和亚硫酸氢钠中的一种或多种。
优选地，单边缩合剂包括丁酮和丁酮衍生物中一种或多种。
优选地，丁酮衍生物包括甲基异丁酮、3-羟基丁酮和3-巯基-2-丁酮中的一种或多种。
优选地，扩联剂包括甲醛和乙醛中的一种或多种。
优选地，甲醛的浓度为37％。
优选地，碱剂为氢氧化钠和氢氧化钾中的一种或多种。
本发明还提供了一种混凝土微沫剂的制备方法，包括如下步骤：
(1)将100～150份磺化剂与200～400份水混合，加入0～100份碱剂调节pH到9.0～11.0，在50～65℃条件下充分搅拌至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液；
(2)控制步骤(1)的温度升至60～70℃，在溶解后的溶液中加入100～200份单边缩合剂和200～400份的扩联剂，并控制温度在95～100℃之间，然后保温4.0～6.0h，保温结束后，补充50～200份水，即得到混凝土微沫剂。
优选地，步骤(1)中，在50～65℃条件下充分搅拌10～30min至至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液。
本发明中混凝土微沫剂的有益效果：
本发明实施例提供的混凝土微沫剂，与现有技术相比，本发明以单边缩合剂及其他组分进行单边缩合反应，以得到一类小分子聚合物的混凝土微沫剂，此外，本发明中的混凝土微沫剂具有气泡稳定性好、受混凝土搅拌时间和存放时间的影响小，且极大改善了混凝土的和易性、流动性和施工性能，具有更高的减水率和性价比。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
下述实施例中的实验方法，如无特殊说明，均为常规方法。下述实施例中所用的试验材料和试剂等，如无特殊说明，均可从商业途径获得。以下实施例中的定量试验，均设置三次重复实验，数据为三次重复实验的平均值或平均值±标准差。
另外，全文中的“和/或”包括三个方案，以A和/或B为例，包括A技术方案、B技术方案，以及A和B同时满足的技术方案；另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。
本发明的实施例提供了一种混凝土微沫剂，以重量份数计，混凝土微沫剂包括：
磺化剂：100～150份；
碱剂：0～100份；
单边缩合剂：100～200份；
扩联剂：200～400份；
水：250～600份。
本发明实施例提供的混凝土微沫剂，与现有技术相比，本发明以单边缩合剂及其他组分进行单边缩合反应，以得到一类小分子聚合物的混凝土微沫剂，此外，本发明中的混凝土微沫剂具有气泡稳定性好、受混凝土搅拌时间和存放时间的影响小，且极大改善了混凝土的和易性、流动性和施工性能，具有更高的减水率和性价比。
在一些实施例中，磺化剂包括亚硫酸盐、焦亚硫酸盐和亚硫酸氢盐中的一种或多种，通过上述磺化剂溶于水后的磺酸基团在水溶液中进行水解，使得混凝土微沫剂反应体系呈碱性，以促进混凝土微沫剂反应体系中各组分进行缩合反应，得到一种小分子聚合物类的混凝土微沫剂，此外，上述磺化剂还能与混凝土微沫剂反应体系中单边缩合剂及扩联剂发生磺化反应，以提供羟基和磺酸基团，进而促进缩合反应的进行。
具体地，磺化剂包括亚硫酸钠、焦亚硫酸钠和亚硫酸氢钠中的一种或多种，以更有效的促进缩合反应的进行。
具体地，亚硫酸钠的纯度大于等于96％，以有效提高混凝土微沫剂反应 体系中的反应效率。
具体地，焦亚硫酸钠的纯度大于等于96％，以有效提高混凝土微沫剂反应体系中的反应效率。
具体地，亚硫酸氢钠的纯度大于等于96％，以有效提高混凝土微沫剂反应体系中的反应效率。
在一些实施例中，单边缩合剂包括丁酮或丁酮类衍生物，丁酮或丁酮类衍生物，在丁酮或丁酮类衍生物的羰基基团的两侧一边为伯碳，即碳上有三个氢，另一边则不是伯碳，这使得丁酮或丁酮类衍生物进行的缩合反应为单边缩合反应，进而使得得到的混凝土微沫剂为小分子聚合物类的混凝土微沫剂。
具体地，丁酮类衍生物包括甲基异丁酮、3-羟基丁酮和3-巯基-2-丁酮中的一种或多种。
在一些实施例中，扩联剂包括甲醛和乙醛中的一种或多种，以有效调节混凝土微沫剂的分子量，得到本发明中的小分子聚合物类的混凝土微沫剂。
在一些实施例中，甲醛的浓度为37％，以更有效的调节混凝土微沫剂的分子量，且浓度为37％的甲醛为能够与混凝土微沫剂反应体系中的其他组分相适应以得到各项性能优越的混凝土微沫剂的浓度，保障甲醛不会过量使用，造成环境污染。
在一些实施例中，乙醛的浓度为40％，以更有效的调节混凝土微沫剂的分子量，且浓度为40％的乙醛为能够与混凝土微沫剂反应体系中的其他组分相适应以得到各项性能优越的混凝土微沫剂的浓度，保障乙醛不会过量使用，达到节能的效果。
在一些实施例中，碱剂为氢氧化钠和氢氧化钾中的一种或多种，在磺化剂中的磺酸基团在水中的水解不能使混凝土微沫剂反应体系达到反应所需的碱性环境的条件下时，碱剂补充调节混凝土微沫剂反应体系中pH为9.0～11.0，以达到反应所需的碱性环境。
在一些实施例中，碱剂包括浓度为50％的氢氧化钠和浓度为50％的氢氧化钾的一种或多种，以有效调节混凝土微沫剂反应体系中pH为9.0～11.0，避免了混凝土微沫剂反应体系中的pH与反应所需的pH不适应。
本发明还提供了一种混凝土微沫剂的制备方法，包括如下步骤，
(1)将100～150份磺化剂与200～400份水混合，加入0～100份碱剂调节pH到9.0～11.0，在50～65℃条件下充分搅拌至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液；
(2)控制步骤(1)的温度升至60～70℃，在溶解后的溶液中加入100～200份单边缩合剂和200～400份的扩联剂，并控制温度在95～100℃之间，然后保温4.0～6.0h，保温结束后，补充50～200份水，即得到混凝土微沫剂。
本发明实施例提供了一种混凝土微沫剂的制备方法，与现有技术相比，在混凝土微沫剂反应体系中加入磺化剂并通过碱剂调节pH到9.0～11.0，然后在50～65℃条件下充分搅拌至至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液，使得混凝土微沫剂反应体系呈碱性环境，以促进混凝土微沫剂反应体系中后续单边缩合反应的进行，并且磺化剂溶于水后产生的磺酸基团与混凝土微沫剂反应体系中单边缩合剂及扩联剂发生磺化反应，以提供羟基和磺酸基团，也能促进后续单边缩合反应的进行；同时，在碱性环境下及上述各项条件下，单边缩合剂与扩联剂在溶解后的溶液中发生单边缩合反应，并补充50～200份水，以调节单边缩合反应完成后的混凝土微沫剂为所需的理想浓度，即得到一种小分子聚合物类的混凝土微沫剂，且浓度为施工所需的理想浓度，本发明中混凝土微沫剂具有气泡稳定性好、受混凝土搅拌时间和存放时间的影响小的优点，且本发明中混凝土微沫剂能够极大改善混凝土的和易性、流动性和施工性能，具有更高的减水率和性价比。
在一些实施例中，步骤(1)中，在50～65℃条件下充分搅拌10～30min至至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液，以使得磺化剂与碱剂充分溶解，增加溶解后的溶液中的稳定性。
在一些实施例中，步骤(2)中，保温结束后，降温至70～75℃，并补充50～200份水，即得到混凝土微沫剂。
以下结合优选实施例对本发明的技术方案作进一步的说明。
实施例1：
(1)将350份水和130份亚硫酸钠混合，加入10份浓度为50％氢氧化钠调节pH到9.0，在50～65℃的条件下充分搅拌20min至磺化剂与碱剂在水中溶解完全，得到溶解后溶液；
(2)控制步骤(1)的温度升至65℃，在溶解后的溶液中加入150份的 丁酮，300份的甲醛，并控制反应温度为96℃，保温4.0h，保温结束后，降温至70℃以下，补充100份水，即得到混凝土微沫剂。
实施例2：
(1)将350份水和100份焦亚硫酸钠混合，加入80份浓度为50％氢氧化钠调节pH到10.0，在50～65℃的条件下充分搅拌20min至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液；
(2)控制步骤(1)的温度升至65℃，在溶解后的溶液中加入160份的3-羟基丁酮，300份的甲醛，并控制反应温度为96℃，保温4.0h，保温结束后，降温至70℃以下，补充50份水，即得到混凝土微沫剂。
实施例3
(1)将350份水和110份亚硫酸氢钠混合，加入50份浓度为50％氢氧化钠调节pH到10.0，在50～65℃的条件下充分搅拌20min至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液；
(2)控制步骤(1)的温度升至68℃，在溶解后的溶液中加入180份的3-巯基-2-丁酮，350份的乙醛，并控制反应温度为96℃，保温5.0h，保温结束后，降温至70℃以下，补充120份水，即得到混凝土微沫剂。
实施例4
(1)将350份水和130份亚硫酸钠混合，加入10份浓度为50％氢氧化钠调节pH到10.0，在50～65℃的条件下充分搅拌20min至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液；
(2)控制步骤(1)的温度升至68℃，在溶解后的溶液中加入100份的丁酮和60份的3-羟基丁酮，300份的甲醛，并控制反应温度为96℃，保温4.0h，保温结束后，降温至70℃以下，补充100份水，即得到混凝土微沫剂。
性能评估
结合实施例1-4，及市售传统混凝土微沫剂，对本发明中混凝土微沫剂的性能进行评估。
首先，将实施例1-4得到的混凝土微沫剂及市售传统混凝土微沫剂加入到各组的混凝土中，并将加入实施例1-4中混凝土微沫剂及市售传统混凝土微沫剂的混凝土存放并搅拌60min，其中，以重量份数计，各组混凝土配合比均如 表1所示，每个组的混凝土均为同样的混凝土，水泥采用南方P.O42.5R水泥，煤灰为II级煤灰，矿粉为S95矿粉，细砂为细度模数为1.2的细砂，机制砂为细度模数为3.0的机制砂，碎石为粒径为5～25的连续级配的碎石，减水剂为PCE聚羧酸减水剂，其中，PCE聚羧酸减水剂的掺量为包括水泥、煤灰、矿粉、细砂、机制砂、碎石及水在内的胶材的总质量的2.0％(折成固为0.20％)，实施例1-4得到的混凝土微沫剂及市售传统混凝土微沫剂掺量均为PCE聚羧酸减水剂掺量的0.1％。根据GB8076-2008《混凝土外加剂》和GBT 50081-2002《普通混凝土力学性能实验方法》，检测其不同的性能指标。结果如表2所示。
表1 C30混凝土配合比
Figure PCTCN2021112824-appb-000001
表2 不同混凝土微沫剂的性能测试
Figure PCTCN2021112824-appb-000002
由表2可知，在掺量相同的情况下，本发明中实施例1-4中的混凝土微沫剂与对比例1中市售传统混凝土微沫剂相比，本发明中的混凝土微沫剂具有更高的混凝土减水率及更优越的和易性；其次，对比例1中样品的含气量在 0min～60min分钟内，由1.0％变为0.2％，然而本发明中，实施例1-4中样品的含气量在0min～60min分钟内，变化趋势并不明显，由上可知，本发明中的混凝土微沫剂具有更高的含气量，且气泡稳定性好，受混凝土搅拌和存放时间的影响小；此外，本发明中实施例1-4中的样品与对比例1中样品在7d到28d内，样品的抗压强度均增加，都具有优越的抗压强度，这可以说明本发明中混凝土微沫剂对混凝土不同期龄的抗压强度无明显影响，且能使得混凝土具有优越的强度，因此，添加了本发明中混凝土微沫剂的混凝土具有高强度的优点。
以上所述仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是在本发明的发明构思下，利用本发明说明书所作的等效结构变换，或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。

Claims (10)

  1. 一种混凝土微沫剂，其特征在于，以重量份数计，所述混凝土微沫剂包括：
    磺化剂：100～150份；
    碱剂：0～100份；
    单边缩合剂：100～200份；
    扩联剂：200～400份；
    水：250～600份。
  2. 根据权利要求1所述的混凝土微沫剂，其特征在于，所述磺化剂包括亚硫酸盐、焦亚硫酸盐和亚硫酸氢盐中的一种或多种。
  3. 根据权利要求2所述的混凝土微沫剂，其特征在于，所述磺化剂包括亚硫酸钠、焦亚硫酸钠和亚硫酸氢钠中的一种或多种。
  4. 根据权利要求1所述的混凝土微沫剂，其特征在于，所述单边缩合剂包括丁酮和丁酮衍生物中一种或多种。
  5. 根据权利要求4所述的混凝土微沫剂，其特征在于，所述丁酮衍生物包括甲基异丁酮、3-羟基丁酮和3-巯基-2-丁酮中的一种或多种。
  6. 根据权利要求1所述的混凝土微沫剂，其特征在于，所述扩联剂包括甲醛和乙醛中的一种或多种。
  7. 根据权利要求6所述的混凝土微沫剂，其特征在于，所述甲醛的浓度为37％。
  8. 根据权利要求1所述的混凝土微沫剂，其特征在于，所述碱剂为氢氧化钠和氢氧化钾中的一种或多种。
  9. 一种混凝土微沫剂的制备方法，其特征在于，包括如下步骤：
    (1)将100～150份磺化剂与200～400份水混合，加入0～100份碱剂调节pH到9.0～11.0，在50～65℃条件下充分搅拌至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液；
    (2)控制步骤(1)的温度升至60～70℃，在所述溶解后的溶液中加入100～200份单边缩合剂和200～400份的扩联剂，并控制温度在95～100℃之间，然后保温4.0～6.0h，保温结束后，补充50～200份水，即得到所述混凝土微沫 剂。
  10. 根据权利要求9所述的制备方法，其特征在于，步骤(1)中，在50～65℃条件下充分搅拌10～30min至至磺化剂与碱剂在水中溶解完全，得到溶解后的溶液。
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