高活性氟碳表面活性剂研究
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摘要
氟碳表面活性剂是一类特种表面活性剂,它的独特性能常被概括为:“三高”、“两憎”、用量少以及复配性能好等优良特点。本文合成了氟碳表面活性剂中间体N-[3-(二甲基氨基)-丙基]-全氟辛基磺酰胺(NFA),考查了温度、溶剂、配比等因素对收率的影响,确定了合成的最佳条件;用合成的中间体NFA制备出了磺基甜菜碱、羧基甜菜碱、双子阳离子以及氧化胺四种氟碳表面活性剂,用红外光谱对产物进行了结构表征,并对表面活性剂的离子类型进行了鉴定;对四种氟碳表面活性剂进行了表面活性的研究,确定了其临界胶束浓度CMC,考查了磺基甜菜碱和羧基甜菜碱的化学稳定性以及耐温抗盐性能;对磺基甜菜碱和羧基甜菜碱氟碳表面活性剂的泡沫性能进行了室内研究,考查了无机盐和温度对泡沫性能的影响以及抗油性;将磺基甜菜碱氟碳表面活性剂分别与阴离子表面活性剂、阳离子表面活性剂以及非离子表面活性剂进行了复配,研究了复合表面活性剂之间的相互作用和复配体系的应用性能,并探讨了表面活性剂种类、体系组成、浓度、温度、无机盐等因素对体系性能的影响。室内研究表明,制备出的氟碳表面活性剂具有表面活性高、临界胶束浓度低、耐温抗盐及稳定性好等特点,在含油量较高的情况下仍有很好的泡沫性能,且与碳氢表面活性剂配伍性好,在油田上具有很高的实际应用价值。
Fluorocarbon surfactant is one of the most important special surfactants, its particular properties are usually included as high surface activity, high heat resistance, high chemical stability; fluoroalkyl is hydrophobic and oleophobic. Fluorocarbon surfactant is the most effective surfactant we ever know, on the one hand, it can reduce the surface tension of water or organic solvent to a very low value; on the other hand, the quantity needed is much less than others. Fluorocarbon surfactants also have well high complex ability. These special capabilities of the fluorocarbon surfactant make it applied widely. In the oilfield, fluorocarbon surfactants have the function that other hydrocarbon surfactants can not substitute. The influence of temperature, solvent, ratio and etc. on the productivity of N-[3-dimethylamido-propyl]perfluoroalkyl sulfonamide are discussed in the paper. So we get the good synthesized condition. Then the sulfoxyneurine, carboxyloxyneurine, Gemini and oxidoamine four fluorocarbon surfactants are synthesized by the intermediate. IR spectrum is taken to confirm their structure, then ion species for the fluorocarbon surfactants are identified by the method of chemical analysis. The surface activity of four fluorocarbon surfactants are designed, confirming their critical micelle concentration, and the effects of temperature and inorganic salts of surface activity are also evaluated. All of them have good chemical stability, temperature tolerance and salt tolerance. Both the effects of inorganic salts, temperature and oil proofness on foam character of two amphoteric fluorocarbon surfactants are researched. These amphoteric fluorocarbon surfactants exhibit very good foaming ability and foam stability and much better foam stability when have the oil.Then the surface activity of the fluorocarbon surfactant with anionic hydrocarbon surfactants、cationic hydrocarbon surfactants and nonionic hydrocarbon surfactant in different ratio are also studied.When it is applied with anionic hydrocarbon surfactants, the effects are better. The influence of the system such as the type of surfactant, system composition, density, temperature, inorganic salt and so on are discussed in the paper.All the results show that the fluorocarbon surfactants have many good characters, such as high surface ability, the low CMC, high temperature tolerance and salt tolerance. The fluorocarbon surfactants still exbit good foam characters when have the high content of oil. When they are applied with hydrocarbon surfactants, the synergic behavior is better. So the flourocarbon surfactants have high actual application in the oilfield.
Fluorocarbon surfactant is one of the most important special surfactants, its particular properties are usually included as high surface activity, high heat resistance, high chemical stability; fluoroalkyl is hydrophobic and oleophobic. Fluorocarbon surfactant is the most effective surfactant we ever know, on the one hand, it can reduce the surface tension of water or organic solvent to a very low value; on the other hand, the quantity needed is much less than others. Fluorocarbon surfactants also have well high complex ability. These special capabilities of the fluorocarbon surfactant make it applied widely. In the oilfield, fluorocarbon surfactants have the function that other hydrocarbon surfactants can not substitute. The influence of temperature, solvent, ratio and etc. on the productivity of N-[3-dimethylamido-propyl]perfluoroalkyl sulfonamide are discussed in the paper. So we get the good synthesized condition. Then the sulfoxyneurine, carboxyloxyneurine, Gemini and oxidoamine four fluorocarbon surfactants are synthesized by the intermediate. IR spectrum is taken to confirm their structure, then ion species for the fluorocarbon surfactants are identified by the method of chemical analysis. The surface activity of four fluorocarbon surfactants are designed, confirming their critical micelle concentration, and the effects of temperature and inorganic salts of surface activity are also evaluated. All of them have good chemical stability, temperature tolerance and salt tolerance. Both the effects of inorganic salts, temperature and oil proofness on foam character of two amphoteric fluorocarbon surfactants are researched. These amphoteric fluorocarbon surfactants exhibit very good foaming ability and foam stability and much better foam stability when have the oil.Then the surface activity of the fluorocarbon surfactant with anionic hydrocarbon surfactants、cationic hydrocarbon surfactants and nonionic hydrocarbon surfactant in different ratio are also studied.When it is applied with anionic hydrocarbon surfactants, the effects are better. The influence of the system such as the type of surfactant, system composition, density, temperature, inorganic salt and so on are discussed in the paper.All the results show that the fluorocarbon surfactants have many good characters, such as high surface ability, the low CMC, high temperature tolerance and salt tolerance. The fluorocarbon surfactants still exbit good foam characters when have the high content of oil. When they are applied with hydrocarbon surfactants, the synergic behavior is better. So the flourocarbon surfactants have high actual application in the oilfield.
引文
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[17] Graciaa A,Creux P,Lachaise J.et al. Competitive Adsorption of Surfactant at Air/Water Interfaces[J].Joural of Colloid and Interface Science,2003,261:233-237
[18]朱顺根.含氟表面活性剂[J].化工生产与技术,1997,(3):1-4
[19]肖进新.氟碳表面活性剂的物化性质及其应用研究.上海:中国科学院上海有机化学研究所博士后研究工作报告,1995:1-24
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[21]孙元宝,魏贤勇,邱贞慧.氟表面活性剂的合成工艺[J].精细石油化工进展,2003,4(3):6-9
[22]牟建海,姜标,解德良.氟表面活性剂在石油和消防领域的应用[J].化工科技市场,2003,26(2):5-9
[23]隋智慧,林冠发.三次采油用表面活性剂的制备与应用及其进展[J].日用化学工业,2003,33(2):105-109
[24] Willian Alan Rendall,Conrad Ayasse,Jaromir Novosad.Surfactant-stabilised foams.GB:2245622A, 1992-08-01
[25]赵福麟.采油用剂[M].东营:石油大学出版社,2000:57-59
[26] Klein H G,Meussdoerffer J N,Niederprum H.Galvanotechnik,1977,68:1045-1058
[27]毛绍裘,汤美芳,顾超.含氟磺基甜菜碱型两性表面活性剂的合成及其集油性能[J].有机氟工业,1994,(2):1-7
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[38] Matsuoka K,Moroi Y.Micellization of fluorinated amphiphiles.Current Opinion In Colloid Interface Science.2003,8(3):227-235
[39] Colgate Palmolive Co.Non-staining antibacterial dentifrice[P].EP:480811.1992-04-15
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[41]陈荣沂.表面活性剂化学与应用[M].北京:纺织工业出版社,1990:89-90
[42]李焰,田娟,陈志启,陈祖兴,等.N-丙基-N-全氟辛基磺酰基甘氨酸盐类表面活性剂的合成方法改进及性能[J].精细化工,2003,20(3):45-67 [43 ]徐国宇,胡春玲.烷基全氟辛基磺酞胺合成工艺研究[J].湖北大学学报(自然科学版),2003,25(2):365-480
[44]郑剑,张应阔,钱万红,等.硫氟酰胺的合成与药效观察[J].医学动物防治,1997,13(5):265-266
[45]黄智,李成海,梁宇宁,等.N,N,一双月桂酞基乙二胺二乙酸钠合成方法的改进[J].精细化工,2002,19(11):621-622
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