CN106179111A - 一种由羧酸盐阴离子表面活性剂和二聚季铵盐形成的粘弹溶液 - Google Patents

一种由羧酸盐阴离子表面活性剂和二聚季铵盐形成的粘弹溶液 Download PDF

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CN106179111A
CN106179111A CN201610562863.7A CN201610562863A CN106179111A CN 106179111 A CN106179111 A CN 106179111A CN 201610562863 A CN201610562863 A CN 201610562863A CN 106179111 A CN106179111 A CN 106179111A
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王丹萍
宋冰蕾
雷岚
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Chongqing Chemical Research Institute Co., Ltd
Chongqing Chemical Research Institute Material Technology Co., Ltd
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Abstract

本发明涉及一种由羧酸盐阴离子表面活性剂和二聚季铵盐形成的粘弹溶液。其中的羧酸盐表面活性剂疏水链较长，但水溶性良好。将该表面活性剂与二聚季铵盐复配后，即可形成一种以阴离子表面活性剂为主体构筑的粘弹溶液。溶液的粘弹性强弱与二聚季铵盐头基之间的联接链长度有关。该溶液可作为一种性能优良的环境友好型产品，可应用于油田压裂液、拖曳减阻剂、日常清洁剂、洗涤剂、分散剂和日用化学品等配方中。

Description

一种由羧酸盐阴离子表面活性剂和二聚季铵盐形成的粘弹 溶液
技术领域
本发明涉及一种表面活性剂和二聚有机盐形成的粘弹溶液，特别涉及一种由羧酸盐型阴离子表面活性剂与二聚季铵盐形成的粘弹溶液，属于表面活性剂科学领域。
背景技术
表面活性剂粘弹溶液在日常生活和工业生产中有着广泛的应用，可用于油田压裂液、拖曳减阻剂和日常清洁剂配方等。表面活性剂粘弹溶液的形成与体系构成密切相关，常见的粘弹溶液体系包括表面活性剂/盐体系，阴阳离子表面活性剂体系和表面活性剂/非离子添加剂体系等。其中，由阴离子表面活性剂为主体构筑的粘弹溶液具有更好的生物相容性，因而具有更为广阔的应用前景。然而，从目前报道的体系来看，以阴离子表面活性剂为主体构筑的粘弹溶液通常需要依赖于某种特殊的分子结构，涉及到较复杂的合成过程，这导致阴离子型表面活性剂粘弹溶液体系形成困难。
表面活性剂粘弹溶液的形成涉及多种因素的协同作用，如表面活性剂的分子结构，反离子的种类，浓度等。从分子排列参数理论可知，通过调节表面活性剂分子疏水链的长度，可增加其疏水基的体积，可以有效减小排列参数的数值，使得分子易于自组装成线型聚集结构；再通过调节反离子的种类与结构，可以进一步优化分子几何。因此，利用合适结构的阴离子表面活性剂并采用上述调控手段，有望构筑出具有粘弹性的新型阴离子表面活性剂溶液体系。
发明内容
为了丰富阴离子表面活性剂粘弹溶液的种类，促进其在相关领域的应用，本发明提供了一种以新型羧酸盐表面活性剂为主体构筑的粘弹溶液体系。将阴离子表面活性剂与二聚季铵盐按照1:2的摩尔比复配，在一定的浓度区间即可形成粘弹溶液。
本发明的技术方案为：一种以阴离子表面活性剂为主体构筑的溶液，是将该表面活性剂与二聚季铵盐按照1:2的摩尔比混合得到。其中的阴离子羧酸盐表面活性剂(C18-Ph-Na)的结构式如下：
该羧酸盐型阴离子表面活性剂的合成路线如下：
二聚季铵盐(N-n-N，n为联接链碳原子数)的分子结构如下：
将羧酸盐型阴离子表面活性剂(C18-Ph-Na)与二聚季铵盐按照1:2的摩尔比配成一定浓度的水溶液，即可获得具有明显粘弹性的溶液。
有益效果
将羧酸盐型阴离子表面活性剂(C18-Ph-Na)与二聚季铵盐复配后即可获得一类以阴离子表面活性剂为主体构筑的粘弹溶液，该溶液具有更好的生物相容性可环境友好性，可应用于油田压裂液，拖曳减阻剂和日常清洁剂配方。
附图说明
图1 C18-Ph-Na的1HNMR谱图。
图2 C18-Ph-Na(100mmol/L)与二聚季铵盐(N-n-N,n＝3,4,6)混合溶液的稳态流变剪切图(C18-Ph-Na:N-n-N＝1:2)。
图3 C18-Ph-Na(100mmol/L)与二聚季铵盐(N-n-N,n＝3,4,6)混合溶液的动态流变剪切图(C18-Ph-Na:N-n-N＝1:2)。
具体实施方式
实施例1:α-溴代十八酸甲酯的合成。将250g(0.879mol)硬脂酸加入1000ml三口瓶中，将温度升至70℃，使固体熔化，在搅拌下缓慢滴加167.1g(1.41mol)亚硫酰氯，之后加入3g碘作为引发剂，升温至90℃，缓慢滴加184.2g(1.153mol)液溴，滴完后继续反应1h。降温至55℃，滴加84.46g(2.626mol)无水甲醇，滴加完后回流4h，冷却至室温，用饱和的亚硫酸钠溶液洗去粗产物中残留的溴素，静置，分出水层。有机层用水洗涤至中性，并用无水硫酸镁干燥，抽滤，收集滤液，对滤液进行两次减压蒸馏，收集208℃-212℃/5mmHg的馏分，即为产物，产率74.5％。
实施例2:α-苯氧基十八酸甲酯的合成。将54.94g(0.40mol)K2CO3和200mL的DMF加入500mL三口瓶中，搅拌0.5h后，缓慢滴加苯酚31.17g(0.33mol)的DMF溶液，升温至80℃，之后滴加50g(0.14mol)溴代硬脂酸甲酯的DMF溶液，继续反应24小时。冷却至室温后，将混合物过滤。将滤液在减压下除去DMF。加入100mL水，用二氯甲烷萃取三次，合并有机层。并将有机层用水洗涤三次，用无水硫酸镁干燥，抽滤后旋转蒸发出全部二氯甲烷。用硅胶柱层析分离，展开剂为石油醚：乙酸乙酯＝10:1(V/V)，最后得终产品，产率为51.5％。
实施例3:α-苯氧基十八酸钠的合成。将18.6g(0.048mol)的α-苯氧基十八酸甲酯和2.08g(0.052mol)的氢氧化钠加入三口烧瓶中，加入250ml乙醇做溶剂，之后加入1.0g(0.056mol)的水，升温至76℃，反应12h。冷却至室温，抽滤，除去不溶于乙醇的杂质，旋转蒸发出全部乙醇，加入适量乙醇重结晶两次，经真空干燥后得终产品α-苯氧基十八酸钠(C18-Ph-Na)，产率87.2％。
实施例4:粘弹表面活性剂溶液的制备。配制若干100mmol/L的C18-Ph-Na溶液，向其中分别加入适量的二聚季铵盐固体，使阴离子表面活性剂与二聚季铵盐的摩尔比为1:2，溶解后即得到系列粘弹表面活性剂溶液。
实施例5:表面活性剂溶液的粘弹性测量。将所得粘弹表面活性剂溶液在25℃下进行流变性能的测试。动态扫描前，先进行应力扫描以确定测试样品的线性粘弹区，所有样品的测试均在线性粘弹区内进行。图2和图3为测试样品的稳态和动态剪切图，可以看出，溶液的粘弹性良好，有显著的应用价值。

Claims (4)

1.一种以阴离子表面活性剂为主体构筑的粘弹溶液，是将一种羧酸盐阴离子表面活性剂与一类二聚季铵盐按照1:2的摩尔比在水溶液中复配后获得。其特征在于，阴离子表面活性剂的浓度范围为50mmol/L-200mmol/L。
2.根据权利要求1所述的一种阴离子表面活性剂，其分子结构如下：
。
3.根据权利要求1所述的一类二聚季铵盐，其分子结构如下：
。
4.根据权利要求1所述的一种阴离子表面活性剂，其特征在于，是按照下式反应得到：
。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107088386A (zh) * 2017-06-14 2017-08-25 江南大学 一种高溶解度的长碳链羧酸盐表面活性剂及其形成的粘弹溶液

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1730144A (zh) * 2004-08-04 2006-02-08 大庆高新区鑫诺精细化工有限公司 羧酸盐表面活性剂、其配方体系以及在三次采油中的应用
US20080027098A1 (en) * 2002-01-15 2008-01-31 Sigma-Tau Industrie Farmaceutiche Riunite S.P.A. Derivatives of alpha-phenylthiocarboxylic and alpha-phenyloxy-carboxylic acids useful for the treatment of diseases responding to PPARalpha activation
CN101973887A (zh) * 2010-09-06 2011-02-16 盐城师范学院 一种双季铵盐的制备方法
CN103611471A (zh) * 2013-12-06 2014-03-05 江南大学 一类含芳香基团的羧酸盐表面活性剂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080027098A1 (en) * 2002-01-15 2008-01-31 Sigma-Tau Industrie Farmaceutiche Riunite S.P.A. Derivatives of alpha-phenylthiocarboxylic and alpha-phenyloxy-carboxylic acids useful for the treatment of diseases responding to PPARalpha activation
CN1730144A (zh) * 2004-08-04 2006-02-08 大庆高新区鑫诺精细化工有限公司 羧酸盐表面活性剂、其配方体系以及在三次采油中的应用
CN101973887A (zh) * 2010-09-06 2011-02-16 盐城师范学院 一种双季铵盐的制备方法
CN103611471A (zh) * 2013-12-06 2014-03-05 江南大学 一类含芳香基团的羧酸盐表面活性剂及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘程、米裕民主编: "《表面活性剂性质理论与应用》", 30 June 2003, 北京：北京工业大学出版社 *
田金年: "《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》", 15 December 2015 *
蒋庆哲等编著: "《表面活性剂科学与应用》", 31 May 2006, 北京：中国石化出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107088386A (zh) * 2017-06-14 2017-08-25 江南大学 一种高溶解度的长碳链羧酸盐表面活性剂及其形成的粘弹溶液
CN107088386B (zh) * 2017-06-14 2019-06-07 江南大学 一种高溶解度的长碳链羧酸盐表面活性剂及其形成的粘弹溶液

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