双-十二醇聚氧乙烯醚甲基羧基甜菜碱的合成及性能

doi:10.16085/j.issn.1000-6613.2015.09.035

摘要/Abstract

摘要： 双十二烷基甲基甜菜碱(diC₁₂B)是一种优良的无碱驱油用表面活性剂,但由于亲油性太强,在水中的溶解性较差,并且在油砂表面具有较大的吸附量。本文试图在diC₁₂B分子中引入EO基团,以改善其性能。为此以溴代十二烷和三缩四乙二醇为原料合成了单分布的十二醇聚氧乙烯(4)醚,再经氯代并与一甲胺和氯乙酸锂反应,最终合成了双十二醇聚氧乙烯(4)醚甲基羧基甜菜碱(diC₁₂EO₄B)。产物经核磁和质谱表征,证明与目标产物的分子结构相符。与diC₁₂B相比,diC₁₂EO₄B在水中的溶解度显著增加,25℃时达到1.5×10^-4mol/L,是diC₁₂B 的3倍左右,45℃下在石英砂/水界面的饱和吸附量是diC₁₂B的70%左右。diC₁₂EO₄B保留了diC₁₂B的高表面活性,如较低的临界胶束浓度,1.6×10^-5mol/L;较高的降低表面张力的效能,g_cmc=29.3mN/m;在空气/水界面具有较大的饱和吸附量,6.5×10^-10mol/cm²;和较小的分子截面积,0.26nm²。diC₁₂EO₄B具有优良的降低油/水界面张力的能力,45℃下单独能将大庆地层水/C₇~C₉正构烷烃界面张力降至10^-3mN/m数量级,将大庆原油/地层水的界面张力降至10^-2mN/m数量级。通过与亲油性表面活性剂diC₁₂B以及C₁₆B复配,能在0.0625~5mmol/L总浓度范围内将大庆原油/地层水的界面张力降至10^-3mN/m数量级,无需加入任何碱或电解质。

关键词: 表面活性剂, 甜菜碱, 合成, 超低界面张力, 吸附

Abstract: Didodecylmethylcarboxyl betaine (diC₁₂B) is an excellent hydrophobic surfactant suitable for surfactant-polymer flooding free of alkali. However,due to strong lipophilicity,diC₁₂B has poor solubility in water and has a relatively high adsorption at sandstone/water interface. In this paper,the diC₁₂B molecule is modified by introducing EO groups into long hydrocarbon chains in the diC₁₂B molecule to improve its properties. Thus didodecylpolyoxyethylene (4) ether methyl carboxyl betaine (diC₁₂EO₄B) was synthesized by using dodecyl bromide and polyethylene glycol (4) as initial materials,followed by etherification,chloration,and then reacted with methyl amine and lithium chloroacetate. The molecular structure of the product was confirmed by ¹H NMR and MS spectra. Compared with diC₁₂B,the solubility of diC₁₂EO₄B in aqueous solution at 25℃ is improved,reaching 1.5×10^-4mol/L,which is three times of that of diC₁₂B,and saturated adsorption at quartz/water interface at 45℃ is only 70% of that of diC₁₂B. diC₁₂EO₄B keeps high surface activity of the diC₁₂B,as reflected by its low cmc,1.6×10^-5mol/L,high effectiveness in reducing surface tension of water,g_cmc=29.3mN/m,high saturated adsorption at air/water interface,6.5×10^-10mol/cm²,and small cross section area in monolayer at air/water interface,0.26nm². diC₁₂EO₄B displays a good ability in reducing oil/water interfacial tension (IFT). At 45℃ it can solely reduce C₇~C₉ alkane/Daqing connate water IFT to 10^-3mN/m magnitude,and reduce Daqing crude oil/connate water IFT to 10^-2mN/m magnitude. By mixing with lipophilic surfactant diC₁₂B and hydrophilic surfactant C₁₆B,diC₁₂EO₄B can reduce Daqing crude oil/connate water IFT to 10^-3mN/m magnitude in a wide total surfactant concentration,from 0.625mmol/L to 5mmol/L at 45℃,without adding any alkali and electrolytes.

Key words: surfactant, fatty alcohol ether betaine, synthesis, ultralow interfacial tension, adsorption

中图分类号:

TQ423.3

胡欣, 宋冰蕾, 崔正刚, 裴晓梅, 蒋建中. 双-十二醇聚氧乙烯醚甲基羧基甜菜碱的合成及性能[J]. 化工进展, 2015, 34(09): 3428-3434.

HU Xin, SONG Binglei, CUI Zhenggang, PEI Xiaomei, JIANG Jianzhong. Synthesis and properties of didodecylpolyoxyethylene ether methyl carboxyl betaine[J]. Chemical Industry and Engineering Progree, 2015, 34(09): 3428-3434.

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