CN108033705B - 一种可作为辅助减水剂的化合物 - Google Patents
一种可作为辅助减水剂的化合物 Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 23
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
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- 238000002360 preparation method Methods 0.000 description 4
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- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明涉及减水剂领域,特别是涉及一种可作为辅助减水剂(即部分替代聚羧酸减水剂)的化合物的新用途。本发明提供一种化合物或盐作为辅助减水剂的用途,所述化合物的结构式为A‑Ba或A‑R‑Ba,其中,A选自阴离子基团,B选自亲水基团。本发明所提供的可用作辅助减水剂的化合物其化学结构简单,作用原理明确,因此易于选用。
Description
技术领域
本发明涉及减水剂领域,特别是涉及一种可作为辅助减水剂(即部分替代聚羧酸减水剂) 的化合物的新用途。
背景技术
聚羧酸减水剂是第三代的高效减水剂(第一代指20世纪六七十年代起使用的萘系和密 胺系减水剂、第二代指20世纪八士年代在萘系和密胺系减水剂基础上与缓凝型减水剂复配得 到的复合产品),于1997年开始推向市场。由于这种减水剂具有更高的减水率和更小的坍落 度损失,尽管其成本较高,市场份额仍然逐渐扩大,已经发展成为主流的减水剂品种。但是, 对于混凝土这样的大宗建筑材料,成本的微小降低一直都是有意义的。在聚羧酸减水剂的生 产制备技术方面,有关聚羧酸减水剂制备的专利申请很多(以聚羧酸减水剂查阅中国专利局 的公开专利,有555条),随着对聚羧酸减水剂合成和生产技术研究的深入,聚羧酸减水剂的 制造成本也已大幅度降低,可能已经达到了极限。因此,进一步降低聚羧酸减水剂的成本, 需要有新的途径。
发明内容
鉴于以上所述现有技术的缺点,本发明的目的在于提供一种辅助减水剂,所述辅助减水 剂可以与聚羧酸减水剂混合使用,从而可以至少部分地替代现有的聚羧酸减水剂,用于解决 现有技术中的问题。
为实现上述目的及其他相关目的,本发明第一方面提供一种化合物或其盐作为减水剂的 用途,所述化合物的结构式如下:
A-Ba或A-R-Ba
其中,A选自阴离子基团;
B选自亲水基团;
R选自烷基、芳香基、或环酯基;
a为正整数。
在本发明一些实施方式中,A选自羧酸基(-COOH)、磺酸基(-SO3H)、或磷酸基 (-PO4-aH3-a)。通式中的a通常可以根据阴离子基团A确定其数值范围,例如,当A选自羧 酸基、或磺酸基等基团时,a为1,再例如,当A选自磷酸基等基团时,a为1、2或3。
在本发明一些实施方式中,R选自C1-C6烷基。
在本发明一些实施方式中,B选自(-OCH2CH2-)mR’或(-OCH(CH3)CH2-)nR’,m≥4,n≥3, 且m、n为正整数,R’选自甲氧基(-OCH3)或羟基(-OH)。所述(-OCH2CH2-)mR’通常为环 氧乙烷齐聚物基团,所述(-OCH(CH3)CH2-)nR’通常为环氧丙烷齐聚物基团。
在本发明一些实施方式中,m=4-100,n=3-10。
本申请所提供的所述化合物中,其中B组成的分子链的总长度通常大于1.5nm,由于水 泥颗粒之间的间距大于2~3nm时,就能够克服相互之间的吸引力而保持分散状态,所以本申 请所提供的所述化合物可以至少部分替代现有的减水剂。
在本发明一些实施方式中,所述用途具体为作为辅助减水剂的用途,更具体为作为聚羧 酸减水剂的辅助减水剂的用途。所述化合物能够对水泥颗粒具有分散作用,从而可以作为辅 助减水剂,所述水泥可以是例如硅酸盐水泥、普通硅酸盐水泥、矿渣硅酸盐水泥、火山灰质 硅酸盐水泥、粉煤灰硅酸盐水泥、复合硅酸盐水泥等。
在本发明一些实施方式中,所述化合物代替聚羧酸减水剂的质量百分数为1~20%。
在本发明一些实施方式中,所述聚羧酸减水剂选自ζ电位大于-17mV,即绝对值小于 17mV的聚羧酸减水剂(PC减水剂)。
在本发明一些实施方式中,所述聚羧酸减水剂为酯类聚羧酸减水剂和/或醚类聚羧酸减水 剂。
本发明第二方面提供一种减水剂,包括如上所述的化合物或其盐和聚羧酸减水剂的复配 物。
在本发明一些实施方式中,减水剂中所述化合物或其盐与聚羧酸减水剂的重量比为1: 4-99。
本发明的发明人经过大量实验,发现了一类价格较低廉的化学物质,它们能够和聚羧酸 减水剂分子在水泥表面产生竞争吸附,从而可以略微减少聚羧酸减水剂在拌合初始阶段在水 泥表面的吸附量,同时,这种化学物质也对水泥颗粒的分散有一定的辅助作用,从而在用量 相当的前提下对减水剂的总体分散减水效果没有明显影响。本申请所提供的这一类价格较低 廉的化学物质或者混合物通常可以作为辅助减水剂,其分子结构具有羧基或其他阴离子基团 和亲水性的基团,前者有助于其在水泥颗粒表面的吸附,后者有助于形成一种水合层,也起 到空间位阻作用。虽然本申请所提供的化合物其作用比大分子聚羧酸减水剂的空间位阻作用 小,但是当其作为辅助减水剂与聚羧酸减水剂配合使用时,聚羧酸减水剂起主要的分散减水 作用,辅助减水剂起次要的分散减水作用,但依旧能够降低聚羧酸减水剂的需求量,减水剂 分散减水效果整体上没有明显变化,从而可以降低聚羧酸减水剂的用量。
本发明所提供的可用作辅助减水剂的化合物其化学结构简单,作用原理明确,因此易于 选用。此外,这一类化合物制备方法简单,成本低廉,且可以与聚羧酸减水剂母液直接混合 使用,具有非常好的产业化前景。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式,本领域技术人员可由本说明书所揭露 的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加 以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精 神下进行各种修饰或改变。
须知,下列实施例中未具体注明的工艺设备或装置均采用本领域内的常规设备或装置。
此外应理解,本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以 存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤,除非另有说明; 还应理解,本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设 备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其 他设备/装置,除非另有说明。而且,除非另有说明,各方法步骤的编号仅为鉴别各方法步骤 的便利工具,而非为限制各方法步骤的排列次序或限定本发明可实施的范围,其相对关系的 改变或调整,在无实质变更技术内容的情况下,当亦视为本发明可实施的范畴。
实施例1
实施例1中使用端羧基聚醚作为辅助减水剂,是甲氧基聚乙二醇用氧化剂(如重铬酸钠与硫酸、硝酸和高 锰酸钾)直接氧化的产物,其分子结构通式为CH3—O—(CH2CH2O)n—CH2COOH。(参见:“邢其毅等, 基础有机化学(上册),高等教育出版社,1980:第428页”)。其规格用聚乙二醇的相对分子量来表示。本 实施例中所替代的聚羧酸减水剂具体为HPEG型醚类减水剂(供货商:上海台界化工,型号:TJ-288), 净浆流动度的测量方法参照国标GB8676-2008、GB8077—2012,相关实验参数和结果具体如表1所示:
表1
实施例2
实施例2中使用磺酸基(硫酸基)及其盐作为阴离子头的水溶性改性聚乙二醇作为辅助 减水剂,其分子结构通式为CH3O—(CH2CH2O)n—SO3Na通过脂肪醇与氯磺酸反应,而后中 和制得(反应式如下:
ROH+CISO3H→ROSO3H+HCI↑
ROSO3H+NaOH→ROSO3Na+H2O参见:“姚蒙正程侣柏王家儒,《精细 化工产品合成原理》,中国石化出版社,1992年04月第1版,第198页”,其规格用端甲 氧基聚乙二醇的相对分子量来表示。本实施例中所替代的聚羧酸减水剂具体为TPEG醚类聚 羧酸减水剂(供货商:江苏博特新材料有限公司,型号:PCA-I),净浆流动度的测试方法参 照实施例1,相关实验参数和结果具体如表2所示:
表2
实施例3
实施例3中使用磷酸基作为阴离子头的水溶性改性聚乙二醇作为辅助减水剂,其分子结 构通式为[HO—(CH2CH2O)n]a—PO4-aH3-a,其中a为1~3的整数。制备方法参阅“王凤洁.不 同分子量聚乙二醇磷酸酯合成条件的研究[A].见:中国洗涤用品工业协会、中国日用化学工 业研究院.2006(第九届)国际表面活性剂/洗涤剂会议论文集[C]:196-200.”,其规格用聚乙 二醇的相对分子量来表示。本实施例中所替代的聚羧酸减水剂具体为HPEG醚类聚羧酸减水 剂(供货商:浙江五龙新材股份有限公司,型号:PC-III),净浆流动度的测试方法参照实施 例1,相关实验参数和结果具体如表3所示:
表3
由实施例1-3可知,本申请所提供的可作为辅助减水剂化合物能够至少部分地替代现有 的聚羧酸减水剂,替代后对于减水剂整体的性能没有明显影响,由于本申请所提供的化合物 相对于现有的聚羧酸减水剂成本更加低廉,所以具有非常好的产业化前景。
综上所述,本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技 术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡 所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等 效修饰或改变,仍应由本发明的权利要求所涵盖。
Claims (6)
1.一种化合物或其盐作为聚羧酸减水剂的辅助减水剂的用途,所述化合物的结构式如下:
A-R-Ba
其中,A选自-COOH;
B选自(-OCH2CH2-)mR’,m=4-100,且m为正整数,R’选自甲氧基;
R选自C1-C6烷基;
a为1。
2.如权利要求1所述的用途,其特征在于,所述化合物代替聚羧酸减水剂的质量百分数为1~20%。
3.如权利要求1所述的用途,其特征在于,所述聚羧酸减水剂选自ζ电位大于-17mV的PC减水剂。
4.如权利要求1所述的用途,其特征在于,所述聚羧酸减水剂为酯类聚羧酸减水剂和/或醚类聚羧酸减水剂。
5.一种减水剂,包括如权利要求1-4任一权利要求所述的化合物或其盐和聚羧酸减水剂的复配物。
6.如权利要求5所述的减水剂,其特征在于,所述化合物或其盐与聚羧酸减水剂的重量比为1:4-99。
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