低聚阳离子季铵盐表面活性剂与磺基两性表面活性剂之间的相互作用
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摘要
为对比研究不同寡聚度的阳离子季铵盐表面活性剂与磺基两性表面活性剂之间的相互作用,合成了一种Gemini阳离子季铵盐表面活性剂Malic-2C12及一种三聚阳离子季铵盐表面活性剂Citric-3C12。通过表面张力技术,分别研究了十二烷基三甲基溴化铵(DTAB)、Malic-2C12及Citric-3C12与磺基两性表面活性剂芥酸酰胺丙基羟磺基甜菜碱(EHSB)之间的相互作用。结果表明,DTAB与EHSB的混合行为接近于理想混合。然而,Malic-2C12或Citric-3C12与EHSB混合体系的临界胶束浓度(CMC)均低于理想混合模型的CMC,表明两种表面活性剂分子在混合胶束中存在协同作用。表面活性剂分子优先进入体相聚集形成混合胶束,而在表面吸附层中的排列变得疏松,导致Malic-2C12或Citric-3C12与EHSB混合体系的表面张力(γCMC)反而高于单一表面活性剂体系。另外,结合相互作用参数结果,发现随着阳离子表面活性剂的寡聚度由1(DTAB)增加至2(Malic-2C12)再到3(Citric-3C12),其与EHSB之间的协同作用逐渐增强,存在协同作用的比例区间逐渐增大,但寡聚度逐级增加所带来的增效逐渐放缓。
In order to study the interaction between the cationic quaternary ammonium surfactant of different oligomeric degrees and the sulfonetaine surfactant,a Gemini cationic quaternary ammonium surfactant Malic-2 C12 and a trimeric cationic quaternary ammounium surfactant Citric-3 C12 were synthesized. The interation of dodecyltrimethylammonium bromide( DTAB),Malic-2 C12,and Citric-3 C12 with sulfobetaine surfactant erucamidopropyl hydroxysultaine( EHSB) was studied respectively by surface tension. The results show that the mixed behavior of DTAB and EHSB exhibits only very small deviations of ideal behavior. However,the critical micelle concentration( CMC) of the mixed systems of Malic-2 C12 or Citric-3 C12 with EHSB becomes lower than the CMC of ideal model,suggesting the presence of synergystic interation between surfactant molecules in the mixed micelle. However,surfactant molecules are more likely to form mixed micelles in the bulk solution of the mixed systems of Malic-2 C12 or Citric-3 C12 with EHSB,and the surfactant molecules are loosely packed in the mixed monolayer,resulting in the higher γCMCof the mixed systems than the γCMCof the single surfactant. Meanwhile,the results of the interaction parameters show that the synergystic interaction gradually becomes stronger as the oligomeric degree of the cationic surfactant increases from 1( DTAB) to 2( Malic-2 C12) and then to 3( Citric-3 C12),and the synergistic molar ratio region gradually becomes larger at the same time. However,the extent of the increasement of the synergistic interaction between cationic surfactant and EHSB becomes smaller as the increasement of the oligomeric degree of the cationci surfactant.
In order to study the interaction between the cationic quaternary ammonium surfactant of different oligomeric degrees and the sulfonetaine surfactant,a Gemini cationic quaternary ammonium surfactant Malic-2 C12 and a trimeric cationic quaternary ammounium surfactant Citric-3 C12 were synthesized. The interation of dodecyltrimethylammonium bromide( DTAB),Malic-2 C12,and Citric-3 C12 with sulfobetaine surfactant erucamidopropyl hydroxysultaine( EHSB) was studied respectively by surface tension. The results show that the mixed behavior of DTAB and EHSB exhibits only very small deviations of ideal behavior. However,the critical micelle concentration( CMC) of the mixed systems of Malic-2 C12 or Citric-3 C12 with EHSB becomes lower than the CMC of ideal model,suggesting the presence of synergystic interation between surfactant molecules in the mixed micelle. However,surfactant molecules are more likely to form mixed micelles in the bulk solution of the mixed systems of Malic-2 C12 or Citric-3 C12 with EHSB,and the surfactant molecules are loosely packed in the mixed monolayer,resulting in the higher γCMCof the mixed systems than the γCMCof the single surfactant. Meanwhile,the results of the interaction parameters show that the synergystic interaction gradually becomes stronger as the oligomeric degree of the cationic surfactant increases from 1( DTAB) to 2( Malic-2 C12) and then to 3( Citric-3 C12),and the synergistic molar ratio region gradually becomes larger at the same time. However,the extent of the increasement of the synergistic interaction between cationic surfactant and EHSB becomes smaller as the increasement of the oligomeric degree of the cationci surfactant.
引文
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14 王佳.一种双子表面活性剂的合成及在采油中的应用[J].科学技术与工程,2012,12(12):2596-2598Wang Jia. Synthesis of a kind of gemini surfactant and the application in oil production[J]. Science Technology and Engineering,2012,12(12):2596-2598
15 郑力军,杨海恩,黎晓茸.双子表面活性剂与原油组分相互作用研究[J].科学技术与工程,2013,13(26):7812-7815Zheng Lijun,Yang Haien,Li Xiaorong. Study on interaction between gemini surfactant and crude oil component[J]. Science Technology and Engineering,2013,13(26):7812-7815
16 杨春鹏,宋昭峥.一种超长链双子表面活性剂压裂液的性能评价[J].科学技术与工程,2017,17(22):208-213Yang Chunpeng,Song Zhaozheng. Performance evaluation of a novel ultra-long-chain gemini surfactant fracturing fluid[J]. Science Technology and Engineering,2017,17(22):208-213
17 Mc Lachlan A A,Marangoni D G. Interactions between zwitterionic and conventional anionic and cationic surfactants[J]. Journal of Colloid and Interface Science,2006,295:243-248
18 Wydro P,Paluch M A. Study of the interaction of dodecyl sulfobetaine with cationic and anionic surfactant in mixed micelles and monolayers at the air/water interface[J]. Journal of Colloid and Interface Science,2005,286:387-391
19 López-Díaz D,García-Mateos I,Velázquez M M. Surface properties of mixed monolayers of sulfobetaines and ionic surfactants[J]. Journal of Colloid and Interface Science,2006,299:858-866
20 侯研博,乔富林,秦冰,等.寡聚度对低聚阳离子季铵盐表面活性剂的聚集行为、油/水界面性能及润湿性的影响[J].石油学报. 2018,34(3):530-537Hou Yanbo,Qiao Fulin,Qin Bing,et al. Effect of degree of oligomerization on aggregation behavior,oil/water interfacial properties and wettability of oligomeric cationic quaternary ammonium surfactant[J]. Acta Petrolei Sinica,2018,34(3):530-537
21 Guo S F,Wang H Y,Shi J,et al. Synthesis and properties of a novel alkyl-hydroxyl-sulfobetaine zwitterionic surfactant for enhanced oil recovery[J]. Journal of Petroleum Exploration and Production Technology,2015,5(3):321-326
22 Ji X L,Tian M Z,Wang Y L,et al. Effects of calcium ions on the solubility and rheological behavior of a C22-tailed hydroxyl sulfobetaine surfactant in aqueous solution[J]. Langmuir,2018,34(1):291-301
23 Luo S Q,Wang Y X,Wang Y L,et al. Synergistic interaction and aggregation behavior in a mixture of a tripolar zwitterionic surfactant and an anionic surfactant[J]. Journal of Surfactants Detergents,2018,21(6):899-908
24 Singh K,Marangoni D G. Synergistic interactions in the mixed micelles of cationic gemini with zwitterionic surfactants:the pH and spacer effect[J]. Journal of Colloid and Interface Science,2007,315:620-626
25 Varade D,Joshi T,Bahadur P,et al. Micellar behavior of mixtures of sodium dodecyl sulfate and dodecyldimethylamine oxide in aqueous solutions[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2005,259:103-109
2 Han Y C,Wang Y L. Aggregation behavior of gemini surfactants and their interaction with macromolecules in aqueous solution[J]. Physical Chemistry Chemical Physics,2011,13(6):1939-1956
3 范雅珣,韩玉淳,王毅琳. Gemini表面活性剂分子结构对其水溶液中聚集行为的影响[J].物理化学学报,2016,32(1):214-226Fan Yaxun,Han Yuchun,Wang Yilin. Effects of molecular structures on aggregation behaviors of gemini surfactants in aqueous solutions[J]. Acta Physico-chimica Sinica,2016,32(1):214-226
4 Menger F M,Keiper J S. Gemini surfactants[J]. Angewandte Chemie International Edition,2000,39:1906-1920
5 In M,Aguerre-Chariol O,Zana R. Closed-looped micelles in surfactant tetramer solutions[J]. Journal of Physical Chemistry B,1999,103(37):7747-7750
6 In M,Bec V,Aguerre-Chariol O,et al. Quaternary ammonium bromide surfactant oligomers in aqueous solution:self-association and microstructure[J]. Langmuir,2000,16(1):141-148
7 Hou Y B,Han Y C,Wang Y L,et al. Aggregation behavior of a tetrameric cationic surfactant in aqueous solution[J]. Langmuir,2010,26:28-33
8 Wu C X,Hou Y B,Wang Y L,et al. Molecular conformation-controlled vesicle/micelle transition of cationic trimeric surfactants in aqueous solution[J]. Langmuir,2010,26:7922-7927
9 Fan Y X,Hou Y B,Wang Y L,et al. Synthesis and aggregation behavior of a hexameric quaternary ammonium surfactant[J]. Langmuir,2011,27:10570-10579
10 Zhou C C,Wang F Y,Wang Y L,et al. Selective antimicrobial activities and action mechanism of micelles self-assembled by cationic oligomeric surfactants[J]. ACS Applied Materials and Interfaces,2016,8:4242-4249
11 侯研博,秦冰,李本高,等.一种非离子型低聚表面活性剂及其制备方法:201410553314. 4[P]. 2016-05-11Hou Yanbo,Qin Bing,Li Bengao,et al. A kind of nonionic oligomeric surfactant and the preparation:201410553314. 4[P]. 2016-05-11
12 李杰,佟威,刘建峰,等.季铵盐型低聚表面活性剂对A3碳钢在盐酸介质中的缓蚀性能[J].科学技术与工程,2013,13(26):7812-7815Li Jie,Tong Wei,Liu Jianfeng,et al. Inhibition behavior of quaternary ammonium oligomeric surfactant for A3 steel in hydrochloric acid[J]. Science Technology and Engineering,2011,11(11):2515-2518
13 谭俊岭,沈一丁,夏冰,等.阳离子表面活性剂提高低渗透油藏注水效率机理[J].科学技术与工程,2017,17(36):166-170Tan Junling,Shen Yiding,Xia Bing,et al. Mechanism of improving injection water efficiency in the low permeable reservoir[J].Science Technology and Engineering,2017,17(36):166-170
14 王佳.一种双子表面活性剂的合成及在采油中的应用[J].科学技术与工程,2012,12(12):2596-2598Wang Jia. Synthesis of a kind of gemini surfactant and the application in oil production[J]. Science Technology and Engineering,2012,12(12):2596-2598
15 郑力军,杨海恩,黎晓茸.双子表面活性剂与原油组分相互作用研究[J].科学技术与工程,2013,13(26):7812-7815Zheng Lijun,Yang Haien,Li Xiaorong. Study on interaction between gemini surfactant and crude oil component[J]. Science Technology and Engineering,2013,13(26):7812-7815
16 杨春鹏,宋昭峥.一种超长链双子表面活性剂压裂液的性能评价[J].科学技术与工程,2017,17(22):208-213Yang Chunpeng,Song Zhaozheng. Performance evaluation of a novel ultra-long-chain gemini surfactant fracturing fluid[J]. Science Technology and Engineering,2017,17(22):208-213
17 Mc Lachlan A A,Marangoni D G. Interactions between zwitterionic and conventional anionic and cationic surfactants[J]. Journal of Colloid and Interface Science,2006,295:243-248
18 Wydro P,Paluch M A. Study of the interaction of dodecyl sulfobetaine with cationic and anionic surfactant in mixed micelles and monolayers at the air/water interface[J]. Journal of Colloid and Interface Science,2005,286:387-391
19 López-Díaz D,García-Mateos I,Velázquez M M. Surface properties of mixed monolayers of sulfobetaines and ionic surfactants[J]. Journal of Colloid and Interface Science,2006,299:858-866
20 侯研博,乔富林,秦冰,等.寡聚度对低聚阳离子季铵盐表面活性剂的聚集行为、油/水界面性能及润湿性的影响[J].石油学报. 2018,34(3):530-537Hou Yanbo,Qiao Fulin,Qin Bing,et al. Effect of degree of oligomerization on aggregation behavior,oil/water interfacial properties and wettability of oligomeric cationic quaternary ammonium surfactant[J]. Acta Petrolei Sinica,2018,34(3):530-537
21 Guo S F,Wang H Y,Shi J,et al. Synthesis and properties of a novel alkyl-hydroxyl-sulfobetaine zwitterionic surfactant for enhanced oil recovery[J]. Journal of Petroleum Exploration and Production Technology,2015,5(3):321-326
22 Ji X L,Tian M Z,Wang Y L,et al. Effects of calcium ions on the solubility and rheological behavior of a C22-tailed hydroxyl sulfobetaine surfactant in aqueous solution[J]. Langmuir,2018,34(1):291-301
23 Luo S Q,Wang Y X,Wang Y L,et al. Synergistic interaction and aggregation behavior in a mixture of a tripolar zwitterionic surfactant and an anionic surfactant[J]. Journal of Surfactants Detergents,2018,21(6):899-908
24 Singh K,Marangoni D G. Synergistic interactions in the mixed micelles of cationic gemini with zwitterionic surfactants:the pH and spacer effect[J]. Journal of Colloid and Interface Science,2007,315:620-626
25 Varade D,Joshi T,Bahadur P,et al. Micellar behavior of mixtures of sodium dodecyl sulfate and dodecyldimethylamine oxide in aqueous solutions[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2005,259:103-109