CN114907239A - 一种烷基醚聚氧乙烯醚苯磺酸及其制备方法和应用 - Google Patents

一种烷基醚聚氧乙烯醚苯磺酸及其制备方法和应用 Download PDF

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CN114907239A
CN114907239A CN202210549643.6A CN202210549643A CN114907239A CN 114907239 A CN114907239 A CN 114907239A CN 202210549643 A CN202210549643 A CN 202210549643A CN 114907239 A CN114907239 A CN 114907239A
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polyoxyethylene ether
ether
alkyl
sulfonic acid
alkyl ether
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卢志敏
刘保
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Guangzhou Langqi Daily Necessities Co ltd
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Guangzhou Lonkey Industrial Co ltd
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Abstract

本发明提供一种烷基醚聚氧乙烯醚苯磺酸及其制备方法和应用，涉及表面活性剂技术领域。本发明的烷基醚聚氧乙烯醚苯磺酸具有如式Ⅰ所示的结构，具有可生物降解、抗硬水性强、刺激性小的优点。本发明的可以通过以下方法制备得到：以脂肪醇聚氧乙烯醚和苯酚为反应物，加入催化剂，反应得到苯烷基醚聚氧乙烯醚；以苯烷基醚聚氧乙烯醚和三氧化硫为反应物，反应得到烷基醚聚氧乙烯醚苯磺酸。本发明的基苯磺酸可作为表面活性剂可用于制备个人清洁护理用品，可降低产品的刺激性，提高生物生物降解和抗硬水性。

Description

一种烷基醚聚氧乙烯醚苯磺酸及其制备方法和应用
技术领域
本发明涉及表面活性剂技术领域，特别是涉及一种烷基醚聚氧乙烯醚苯磺酸及其制备方法和应用，尤其是在个人清洁护理用品中的应用。
背景技术
烷基苯磺酸
Figure BDA0003654245600000011
其中R＝C11～C13)是一种重要的阴离子表面活性剂，常用作洗涤剂的原料，生产烷基苯磺酸的钠盐、铵盐和乙醇胺盐等。烷基苯磺酸盐是烷基苯磺酸的中和产物，也是一种重要的阴离子表面活性剂，烷基苯磺酸盐主要包括直链烷基苯磺酸盐(LAS)和支链烷基苯磺酸盐(ABS)。
由于生物降解性差，支链烷基苯磺酸盐已逐渐被直链烷基苯磺酸盐所取代。直链烷基苯磺酸盐的去污力强、起泡能力和泡沫稳定性好，并且在酸性、碱性甚至氧化剂溶液中都具有较好的稳定性，而且其来源充足、制造工艺成熟、成本低，是一种优良的洗涤剂和泡沫剂。直链烷基苯磺酸盐作为洗涤剂中的活性物，具有易喷雾干燥成型的特点，非常适合于制作洗衣粉，也可适量添加于香波、泡沫浴等洗浴液中，还可作为清洗剂、染色助剂，以及金属清洗、造纸工业的脱墨剂的原料。
但是，直链烷基苯磺酸盐也存在一些缺陷，例如对水的硬度敏感，遇到硬水洗涤能力迅速降低，易与水中的钙镁离子反应生成有机沉积物并残留在衣物上，有机沉积物会降低织物的性能，例如增大织物的疏水性，降低毛细效应，降低衣物的气候调节性，加剧织物存留污迹。此外，直链烷基苯磺酸盐作为个人护理原料，相比于脂肪醇硫酸盐、脂肪醇聚氧乙烯醚硫酸盐，具有更强的刺激性，导致其用量和适用范围受限。
烷基酚聚氧乙烯醚
Figure BDA0003654245600000012
常用于替代直链烷基苯磺酸盐，烷基酚聚氧乙烯醚经过初步生物降解后得到烷基酚，而烷基酚也难以生物降解。烷基酚聚氧乙烯醚硫酸钠
Figure BDA0003654245600000013
虽然具有良好的乳化、匀染、渗透、润湿效果，但也同样存在难以生物降解的问题。
发明内容
基于此，有必要针对上述问题，提供一种烷基醚聚氧乙烯醚苯磺酸，具有可生物降解、抗硬水性强、刺激性小的优点。
一种烷基醚聚氧乙烯醚苯磺酸，具有如式Ⅰ所示的结构：
Figure BDA0003654245600000021
其中，R为C8-C16直链烷基或支链烷基，n选自1～3。
上述烷基醚聚氧乙烯醚苯磺酸，具有较好的生物降解性和抗硬水能力，作为表面活性剂刺激性小；该烷基醚聚氧乙烯醚苯磺酸不同于现有的烷基苯磺酸和烷基酚聚氧乙烯醚，其苯环上没有烷基取代基，使其具有良好的表面活性和渗透性，有望取代烷基酚聚氧乙烯醚在工业洗涤剂中的应用。
本发明还提供一种上述烷基醚聚氧乙烯醚苯磺酸的制备方法，通过式Ⅱ所示的路线合成：
Figure BDA0003654245600000022
S1、以脂肪醇聚氧乙烯醚和苯酚为反应物，加入催化剂，反应得到苯烷基醚聚氧乙烯醚；
S2、以苯烷基醚聚氧乙烯醚和三氧化硫为反应物，反应得到如式Ⅰ所示的烷基醚聚氧乙烯醚苯磺酸。
在其中一个实施例中，S1中的催化剂为MgO负载金属基催化剂，负载的金属选自：锌、镍、钛中的一种或两种以上，金属的负载量为MgO重量的3～8％。
在其中一个实施例中，负载的金属为锌、镍、钛中的两种，两种金属的质量比为1：(0.33～3)。
在其中一个实施例中，S1中反应温度为200～300℃，压力为1.0～2.0Mpa。优选地，S1中反应温度为220～280℃，压力为1.2～1.5Mpa。
在其中一个实施例中，脂肪醇聚氧乙烯醚与苯酚的物质的量之比为1：(0.5～5)。优选地，脂肪醇聚氧乙烯醚与苯酚的物质的量之比为1：(0.6～1.5)
在其中一个实施例中，所述S2具体为：在磺化反应器进行反应，取苯烷基醚聚氧乙烯醚和三氧化硫-空气混合气体混合，三氧化硫-空气混合气体中三氧化硫的浓度为4～6vt％，苯烷基醚聚氧乙烯醚与三氧化硫的物质的量之比为(1.02～1.04)：1，三氧化硫-空气混合气体的进气温度为48～58℃，用循环冷却水对磺化反应器进行冷却，使磺化反应器出口处气体温度为43～48℃。
在其中一个实施例中，循环冷却水的温度为26～30℃。
本发明还提供一种烷基醚聚氧乙烯醚苯磺酸盐，具有如式Ⅲ所示的结构：
Figure BDA0003654245600000031
其中，R为C8-C16直链烷基或支链烷基，n选自1～3，M选自：Na+、K+、NH4 +、C2H7NOH+、C4H11NO2H+、C6H15NO3H+、C3H9ONH+。
上述烷基醚聚氧乙烯醚苯磺酸盐，虽结构与烷基酚聚氧乙烯醚硫酸盐具有一定的相似性，但其不仅具有良好的乳化效果，而且降解后不产生烷基酚，生物降解性与常规的直链烷基苯磺酸钠相当。
本发明还提供一种上述烷基苯磺酸盐的制备方法，以碱性溶液和本发明的烷基醚聚氧乙烯醚苯磺酸为原料，经中和反应，得到烷基苯磺酸盐。
在其中一个实施例中，所述碱溶液选自：氢氧化钠溶液、氢氧化钾溶液、氨水、醇氨在其中一个实施例中，所述醇胺选自：单乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺。
本发明还提供一种上述烷基醚聚氧乙烯醚苯磺酸或烷基醚聚氧乙烯醚苯磺酸盐在制备洗涤剂中的应用。
与现有技术相比，本发明具有以下有益效果：
本发明的烷基醚聚氧乙烯醚苯磺酸，具有可生物降解、抗硬水性强、刺激性小的优点。本发明的烷基醚聚氧乙烯醚苯磺酸盐不仅具有良好的乳化效果，而且降解后不产生烷基酚，生物降解性与常规的直链烷基苯磺酸钠相当。本发明的烷基醚聚氧乙烯醚苯磺酸和烷基醚聚氧乙烯醚苯磺酸盐作为表面活性剂用于制备个人清洁护理用品，可提高个人清洁护理用品的抗硬水性强和可生物降解，同时减少刺激性。
具体实施方式
为了便于理解本发明，下面将结合较佳的实施例对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
实施例1
一种烷基醚聚氧乙烯醚苯磺酸，其结构式如式Ⅰ所示，R为C16H33(2-甲基-十五烷基)，n为1。其制备方法如下：
(1)将物质的量之比为2：1的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量3％的MgO负载金属基催化剂(负载量为MgO重量的3％，负载金属为Zn和Ti，二者的质量比为1：3)，混合均匀后，控制温度为295～300℃，压强为1.0～1.1Mpa，反应40～60min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为72％。
(2)取苯烷基醚聚氧乙烯醚置于膜式磺化反应器，通入三氧化硫-空气混合气体，三氧化硫-空气混合气体中三氧化硫的浓度为5vt％，磺化反应器内苯烷基醚聚氧乙烯醚与三氧化硫的物质的量之比为1：1，三氧化硫-空气混合气体的温度为50℃，反应过程中用循环冷却水对磺化反应器进行冷却，使磺化反应器出口处的气体温度为45℃，反应完成后，经老化得到烷基醚聚氧乙烯醚苯磺酸。
一种烷基醚聚氧乙烯醚苯磺酸异丙醇胺，采用实施例1的烷基醚聚氧乙烯醚苯磺酸制备得到，具体包括以下步骤：取异丙醇胺和烷基醚聚氧乙烯醚苯磺酸，异丙醇胺与烷基醚聚氧乙烯醚苯磺酸的物质的量之比为1:1，一边搅拌一边向异丙醇胺中加入烷基醚聚氧乙烯醚苯磺酸，中和反应完成后，得到烷基醚聚氧乙烯醚苯磺酸异丙醇胺。反应式如下。
Figure BDA0003654245600000041
实施例2
一种烷基醚聚氧乙烯醚苯磺酸，其结构式如式Ⅰ所示，R为C10H21直链烷基，n为2。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为1：2的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量6％的MgO负载金属基催化剂(负载量为MgO重量的8％，负载金属为Zn和Ni，二者的质量比为3：1)，混合均匀后，控制温度为200～205℃，压强为1.9～2.0Mpa，反应50～70min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为71％。
一种烷基醚聚氧乙烯醚苯磺酸钾，采用实施例2的烷基醚聚氧乙烯醚苯磺酸制备得到，具体包括以下步骤：取氢氧化钾溶液(质量浓度15％)和实施例2的烷基醚聚氧乙烯醚苯磺酸，氢氧化钾与烷基醚聚氧乙烯醚苯磺酸的物质的量之比为1:1，一边搅拌一边向氢氧化钾溶液中加入烷基醚聚氧乙烯醚苯磺酸，中和反应完成后，得到烷基醚聚氧乙烯醚苯磺酸钾。反应式如下。
Figure BDA0003654245600000042
实施例3
一种烷基醚聚氧乙烯醚苯磺酸，其结构式如式Ⅰ所示，R为C8H17直链烷基，n为3。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为1.5：1的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量4％的MgO负载金属基催化剂(负载量为MgO重量的8％，负载金属为Zn和Ti，二者的质量比为1：2)，混合均匀后，控制温度为275～280℃，压强为1.2～1.3Mpa，反应45～65min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为84％。
一种烷基醚聚氧乙烯醚苯磺酸钠，采用实施例3的烷基醚聚氧乙烯醚苯磺酸制备得到，具体包括以下步骤：取氢氧化钠溶液(质量浓度15％)和烷基醚聚氧乙烯醚苯磺酸，氢氧化钠与烷基醚聚氧乙烯醚苯磺酸的物质的量之比为1:1，一边搅拌一边向氢氧化钠溶液中加入烷基醚聚氧乙烯醚苯磺酸，中和反应完成后，得到烷基醚聚氧乙烯醚苯磺酸钠。反应式如下。
Figure BDA0003654245600000051
实施例4
一种烷基醚聚氧乙烯醚苯磺酸，其结构式如式Ⅰ所示，R为C14H29直链烷基，n为2。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为1：1.5的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量5％的MgO负载金属基催化剂(负载量为MgO重量的6％，负载金属为Zn和Ti，二者的质量比为2：1)，混合均匀后，控制温度为220～225℃，压强为1.4～1.5Mpa，反应40～60min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为87％。
一种烷基醚聚氧乙烯醚苯磺酸单乙醇胺，采用实施例4的烷基醚聚氧乙烯醚苯磺酸制备得到，具体包括以下步骤：取单乙醇胺和烷基醚聚氧乙烯醚苯磺酸，单乙醇胺与烷基醚聚氧乙烯醚苯磺酸的物质的量之比为1:1，一边搅拌一边向单乙醇胺中加入烷基醚聚氧乙烯醚苯磺酸，中和反应完成后，得到烷基醚聚氧乙烯醚苯磺酸单乙醇胺。反应式如下。
Figure BDA0003654245600000052
实施例5
一种烷基醚聚氧乙烯醚苯磺酸，其结构式与实施例1的区别在于n为2。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为1：1的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量4.2％的MgO负载金属基催化剂(负载量为MgO重量的5％，负载金属为Ti和Ni，二者的质量比为1：1)，混合均匀后，控制温度为260～265℃，压强为1.3～1.4Mpa，反应50～70min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为86％。
实施例6
一种烷基醚聚氧乙烯醚苯磺酸，其结构式如式Ⅰ所示，R为C12H25直链烷基，n为3。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为1.2：1的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量4.5％的MgO负载金属基催化剂(负载量为MgO重量的4.5％，负载金属为Zn和Ti，二者的质量比为3：4)，混合均匀后，控制温度为250～255℃，压强为1.25～1.35Mpa，反应45～65min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为83％。
一种烷基醚聚氧乙烯醚苯磺酸二乙醇胺，采用实施例6的烷基醚聚氧乙烯醚苯磺酸制备得到，具体包括以下步骤：取二乙醇胺和烷基醚聚氧乙烯醚苯磺酸，单乙醇胺与烷基醚聚氧乙烯醚苯磺酸的物质的量之比为1:1，一边搅拌一边向单乙醇胺中加入烷基醚聚氧乙烯醚苯磺酸，中和反应完成后，得到烷基醚聚氧乙烯醚苯磺酸二乙醇胺。反应式如下。
Figure BDA0003654245600000061
实施例7
一种烷基醚聚氧乙烯醚苯磺酸，其结构式与实施例1相同。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为4：5的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量4.8％的MgO负载金属基催化剂(负载量为MgO重量的5.5％，负载金属为Zn和Ni，二者的质量比为3：2)，混合均匀后，控制温度为230～235℃，压强为1.3～1.5Mpa，反应55～75min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为82％。
实施例8
一种烷基醚聚氧乙烯醚苯磺酸，其结构式与实施例1的区别在于n为3。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为1.8：1的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量3.5％的MgO负载金属基催化剂(负载量为MgO重量的7％，负载金属为Ti和Zn，二者的质量比为2：5)，混合均匀后，控制温度为210～215℃，压强为1.6～1.7Mpa，反应45～65min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为70％。
实施例9
一种烷基醚聚氧乙烯醚苯磺酸，其结构式与实施例1相同。其制备方法与实施例1基本相同，区别在于步骤(1)：将物质的量之比为3：5的苯酚和脂肪醇聚氧乙烯醚混合，加入苯酚质量5.5％的MgO负载金属基催化剂(负载量为MgO重量的3.5％，负载金属为Ni和Zn，二者的质量比为2.5：1)，混合均匀后，控制温度为285～287℃，压强为1.7～1.8Mpa，反应40～60min，得到苯烷基醚聚氧乙烯醚，经检测脂肪醇聚氧乙烯醚的转化率为75％。
实施例10～17
实施例10～17均为个人清洁剂，各实施例的原料组成和各组成的质量分数占比如表1所示。
个人清洁剂的制备方法包括以下步骤：
(1)将表面活性剂与适量水混合，搅拌至表面活性剂完全溶解；
(2)加入保湿剂，搅拌至完全溶解；配方表中不含保湿剂的略过此步骤；
(3)加入柠檬酸，调节pH为5.5～6.5；
(4)添加氯化钠，搅拌至完全溶解；配方表中不含氯化钠的略过此步骤；
(5)保证温度在45℃以下，加入适量香精，搅拌均匀，降至常温，即得。
表1个人清洁剂的原料和配比(wt％)
Figure BDA0003654245600000071
Figure BDA0003654245600000081
注：表中烷基醚聚氧乙烯醚苯磺酸钠、烷基醚聚氧乙烯醚苯磺酸铵、烷基醚聚氧乙烯醚苯磺酸异丙醇氨、烷基醚聚氧乙烯醚苯磺酸单乙醇胺、烷基醚聚氧乙烯醚苯磺酸三乙醇胺均为本发明的烷基醚聚氧乙烯醚苯磺酸盐。
实验例1
取实施例1和实施例3的烷基醚聚氧乙烯醚苯磺酸盐作为表面活性剂，测试其生物降解性、抗硬水性、刺激性。同时，分别以常规直链十二烷基苯磺酸钠、烷基酚聚氧乙烯醚磺酸钠和脂肪醇聚氧乙烯醚硫酸钠作为对照组。
生物降解性以总BOD值消除率(％)来表征，当BOD值在50％以上，可以认为被测物质基本上达到了全部的生物降解。
抗硬水以表面活性剂在硬水中的发泡能力来表征，依照GB/T 13173-2021中的第11章进行检测，表面活性剂浓度为0.375g/L，水硬度为400ppm，水温(40±0.5)℃。
表面活性剂的刺激性测试采用玉米醇溶蛋白(Zein)法。Zein是一种黄色的玉米蛋白，几乎不溶于水，它的结构与皮肤和头发中存在的角蛋白相似。Zein会与刺激性的物质，如表面活性剂溶液等，发生反应，从而变性溶解。较强刺激性的表面活性剂比弱刺激性的表面活性剂更容易引起Zein的变性，令Zein的溶解增加。用Zein的溶解的量代表表面活性剂或配方的皮肤刺激性。取待测样品，配成活性物质量分数为1％的溶液。取100g溶液，逐次加入0.5g的Zein至不能溶解后，搅拌2小时，然后过滤。将滤纸和沉淀置于45℃烘箱下过夜干燥，称重，并计算溶解的Zein的量。溶解的Zein的量越大，刺激性越大。
测试结果如下表所示：
表2性能测试结果
Figure BDA0003654245600000091
从以上结果可以看出，本发明的烷基醚聚氧乙烯醚苯磺酸盐具有较好的生物降解性，抗硬水性强，刺激性低。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

1.一种烷基醚聚氧乙烯醚苯磺酸，其特征在于，具有如式Ⅰ所示的结构：
Figure FDA0003654245590000011
其中，R为C8-C16直链烷基或支链烷基，n选自1～3。
2.一种权利要求1所述的烷基醚聚氧乙烯醚苯磺酸的制备方法，其特征在于，通过式Ⅱ所示的路线合成：
Figure FDA0003654245590000012
S1、以脂肪醇聚氧乙烯醚和苯酚为反应物，加入催化剂，反应得到苯烷基醚聚氧乙烯醚；
S2、以苯烷基醚聚氧乙烯醚和三氧化硫为反应物，反应得到如式Ⅰ所示的烷基苯磺酸。
3.根据权利要求2所述的制备方法，其特征在于，S1中的催化剂为MgO负载金属基催化剂，负载的金属选自：锌、镍、钛中的一种或两种以上，金属的负载量为MgO重量的3～8％。
4.根据权利要求2所述的制备方法，其特征在于，S1中反应温度为200～300℃，压力为1.0～2.0Mpa，脂肪醇聚氧乙烯醚与苯酚的物质的量之比为1：(0.5～5)。
5.根据权利要求4所述的制备方法，其特征在于，S1中反应温度为220～280℃，压力为1.2～1.5Mpa，脂肪醇聚氧乙烯醚与苯酚的物质的量之比为1：(0.6～1.5)。
6.根据权利要求2所述的制备方法，其特征在于，所述S2具体为：在磺化反应器进行反应，取苯烷基醚聚氧乙烯醚和三氧化硫-空气混合气体混合，三氧化硫-空气混合气体中三氧化硫的浓度为4～6vt％，苯烷基醚聚氧乙烯醚与三氧化硫的物质的量之比为(1.02～1.04)：1，三氧化硫-空气混合气体的进气温度为48～58℃，用循环冷却水对磺化反应器进行冷却，使磺化反应器出口处气体温度为43～48℃。
7.一种烷基醚聚氧乙烯醚苯磺酸盐，其特征在于，具有如式Ⅲ所示的结构：
Figure FDA0003654245590000013
Figure FDA0003654245590000021
其中，R为C8-C16直链烷基或支链烷基，n选自1～3，M选自：Na+、K+、NH4 +、C2H7NOH+、C4H11NO2H+、C6H15NO3H+、C3H9ONH+。
8.一种权利要求7所述的烷基醚聚氧乙烯醚苯磺酸盐的制备方法，其特征在于，以碱性溶液和权利要求1所述的烷基醚聚氧乙烯醚苯磺酸为原料，经中和反应得到烷基苯磺酸盐。
9.根据权利要求8所述的制备方法，其特征在于，所述碱溶液选自：氢氧化钠溶液、氢氧化钾溶液、氨水、醇胺溶液。
10.一种权利要求1所述的烷基醚聚氧乙烯醚苯磺酸或权利要求7所述的烷基醚聚氧乙烯醚苯磺酸盐在制备个人清洁护理用品中的应用。
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US4923635A (en) * 1987-07-06 1990-05-08 Colgate-Palmolive Company Liquid detergent composition containing alkylbenzene sulfonate, alkyl ethanol ether sulfate, alkanolamide foam booster and magnesium and triethanolammonium ions
CN101185866A (zh) * 2006-11-17 2008-05-28 天津科技大学 双子阴离子表面活性剂及其制备方法
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