叔胺型响应表面活性剂的合成及性能研究

doi:10.3969/j.issn.2097-2806.2023.11.002

摘要/Abstract

摘要：

以油酸和N, N-二甲基-1,3-丙二胺为原料，氟化钠为催化剂，合成了一种具有CO₂响应性的长链叔胺（油酸酰胺丙基二甲基叔胺（DMOA）），测定了其通入CO₂和N₂下的电导率，证实了合成的DMOA溶液具有CO₂响应性能。测定了在通入CO₂下DMOA与反离子复配的表面张力，发现将DMOA与二元反离子草酸钠复配能显著降低溶液的表面张力。研究了DMOA与草酸钠复配体系的黏度的CO₂响应性能，结果表明，复配体系能够显著提高体系的黏度，并具有CO₂响应性和循环可逆性。研究了复配体系的起泡性能和在石蜡膜上的接触角，发现在通入了CO₂条件下，复配体系能够降低起泡性能和与疏水表面的接触角。

关键词: 开关表面活性剂, CO₂开关, 可逆响应, 叔胺基, 反离子

Abstract:

A CO₂-responsive surfactant with good surface activity was obtained, which was a long-chain tertiary amine （DMOA） with CO₂ responsiveness. It was synthesized by bimolecular nucleophilic substitution reaction using oleic acid and N, N-dimethyl-1,3-propanediamine as raw materials and sodium fluoride as catalyst. Its conductivity was measured on a conductivity meter under the passage of CO₂ and N₂, and the experimental results confirmed that the solution of synthesized DMOA had CO₂-responsive properties. The surface tension of DMOA compounded with counterions was measured and its critical micelle concentration was determined. It was found that the combination of DMOA with dicarboxylic counterions such as sodium oxalate could significantly reduce the surface tension of the solution, and the critical micelle concentration of the compounded system was also reduced compared with other systems. The CO₂-responsive behavior of the viscosity of the DMOA-sodium oxalate system was studied on a rheometer. The results showed that the compounded system could significantly increase the viscosity of the system, exhibiting CO₂-responsiveness and cyclic reversibility. The foaming performance of the compounded system was investigated, and the contact angle between its aqueous solution and paraffin wax was investigated. It was found that the compounded system exhibited lower foaming performance but smaller contact angle on lipophilic surface after the introduction of CO₂.

Key words: switchable surfactant, CO₂ switching, reversible response, tertiary amine group, counter-ion

中图分类号:

TQ423

张鑫, 张光华, 孙棋, 李慧, 唐明旋, 郭泽华. 叔胺型响应表面活性剂的合成及性能研究[J]. 日用化学工业（中英文）, 2023, 53(11): 1250-1256.

Zhang Xin, Zhang Guanghua, Sun Qi, Li Hui, Tang Mingxuan, Guo Zehua. Study on the synthesis and performance of a responsive surfactant of tertiary amine type[J]. China Surfactant Detergent & Cosmetics, 2023, 53(11): 1250-1256.

图/表 6

参考文献 25

[1]	Kraume M, Enders S, Drews A, et al. Integrated chemical processes in liquid multiphase systems: from chemical reaction to process design and operation[M]. De Gruyter, 2022.
[2]	Su X, Jessop P G, Cunningham M F. Switchable surfactants at the polystyrene-water interface: effect of molecular structure[J]. Green Materials, 2014, 2 (2) : 69-81. doi: 10.1680/gmat.13.00015
[3]	Brown P, Butts C P, Eastoe J. Stimuli-responsive surfactants[J]. Soft Matter, 2013, 9 (8) : 2365-2374. doi: 10.1039/c3sm27716j
[4]	Baul U, Dzubiella J. Structure and dynamics of responsive colloids with dynamical polydispersity[J]. Journal of Physics: Condensed Matter, 2021, 33 (17) : 174002. doi: 10.1088/1361-648X/abdbaa
[5]	Muratalin M, Luckham P F, Esimova A, et al. Study of N-isopropylacrylamide-based microgel particles as a potential drug delivery agents[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2017, 532: 8-17. doi: 10.1016/j.colsurfa.2017.07.075
[6]	Yan Z H, Dai C L, Zhao M W, et al. Multi-responsive wormlike micelles based on N-alkyl-N-methylpiperidinium bromide cationic surfactant[J]. Journal of Surfactants and Detergents, 2015, 18 (5) : 739-746. doi: 10.1007/s11743-015-1718-2
[7]	Brown P, Butts C P, Eastoe J. Stimuli-responsive surfactants[J]. Soft Matter, 2013, 9 (8) : 2365-2374. doi: 10.1039/c3sm27716j
[8]	Zhou B B, Kang W L, Yang H B, et al. Alkyl chain length influence of hydrotrope on the pH responsiveness of surfactant aggregates based on dynamic imine bond[J]. Journal of Molecular Liquids, 2022, 360: 119465. doi: 10.1016/j.molliq.2022.119465
[9]	Chu Z L, Feng Y J. pH-switchable wormlike micelles[J]. Chemical Communications, 2010, 46 (47) : 9028-9030. doi: 10.1039/c0cc02415e pmid: 21052582
[10]	Pei X M, Wu J H, Zou X Y, et al. The switching behavior of CO₂/N₂ responsive emulsion systems formed by an amine functionalized quaternary ammonium surfactant[J]. Journal of Molecular Liquids, 2022, 363: 119915. doi: 10.1016/j.molliq.2022.119915
[11]	Wu X P, Jiang S H, Dai C L. Analysis of the performance of CO₂-responsive clean fracturing fluid and its transformation mechanism[J]. Oilfield Chemistry, 2021, 38 (4) : 608-613.
[12]	Kim D, Sakamoto H, Matsuoka H, et al. Complex formation of sulfobetaine surfactant and ionic polymers and their stimuli responsivity[J]. Langmuir, 2020, 36 (43) : 12990-13000. doi: 10.1021/acs.langmuir.0c02323 pmid: 33095985
[13]	Lencina M S, Miconi E F, Leyes M D F, et al. Effect of surfactant concentration on the responsiveness of a thermoresponsive copolymer/surfactant mixture with potential application on “Smart” foams formulations[J]. Journal of Colloid and Interface Science, 2018, 512: 455-465. doi: 10.1016/j.jcis.2017.10.090
[14]	Liu Y S, Zhang H J, Zhang W Q, et al. Charge density overcomes steric hindrance of ferrocene surfactant in switchable oil-in-dispersion emulsions[J]. Angewandte Chemie, 2023, 135 (5) : e202210050. doi: 10.1002/ange.v135.5
[15]	Chen H, Zhu B, Zhang Y M, et al. Effect of selenium-position on the redox responsivity of isomeric selenium-containing anionic surfactants[J]. Journal of Surfactants and Detergents, 2022, 25 (2) : 227-234. doi: 10.1002/jsde.v25.2
[16]	Guo J, Zhang H Y, Zhou Y, et al. Light-controlled reversible self-assembly of nanorod suprastructures[J]. Chemical Communications, 2017, 53 (45) : 6089-6092. doi: 10.1039/c7cc03280c pmid: 28530009
[17]	Tian T, Song Y Y, Wang J Q, et al. Small-molecule-triggered and light-controlled reversible regulation of enzymatic activity[J]. Journal of the American Chemical Society, 2016, 138 (3) : 955-961. doi: 10.1021/jacs.5b11532 pmid: 26741151
[18]	Brown P, Bushmelev A, Butts C P, et al. Magnetic control over liquid surface properties with responsive surfactants[J]. Angewandte Chemie, 2012, 124 (10) : 2464-2466. doi: 10.1002/ange.v124.10
[19]	Brown P, Khan A M, Armstrong J P, et al. Magnetizing DNA and proteins using responsive surfactants[J]. Advanced Materials, 2012, 24 (46) : 6244-6247. doi: 10.1002/adma.v24.46
[20]	Yang J S, Li J F, Dong H B. CO₂-responsive polymer surfactant formed by noncovalent binding between dimethyl-dodecylamine and alginate[J]. Polymer International, 2019, 68 (4) : 661-666. doi: 10.1002/pi.2019.68.issue-4
[21]	Heldebrant D J, Koech P K, Ang M T C, et al. Reversible zwitterionic liquids, the reaction of alkanol guanidines, alkanol amidines, and diamines with CO₂[J]. Green Chemistry, 2010, 12 (4) : 713-721. doi: 10.1039/b924790d
[22]	Scott L M, Robert T, Harjani J R, et al. Designing the head group of CO₂-triggered switchable surfactants[J]. Rsc Advances, 2012, 2 (11) : 4925-4931. doi: 10.1039/c2ra01242a
[23]	Blauwhoff P M M, Versteeg G F, Van S W P M. A study on the reaction between CO₂ and alkanolamines in aqueous solutions[J]. Chemical Engineering Science, 1983, 38 (9) : 1411-1429. doi: 10.1016/0009-2509(83)80077-3
[24]	Feng D, Zhang Y M, Chen Q S, et al. Synthesis and surface activities of amidobetaine surfactants with ultra-long unsaturated hydrophobic chains[J]. Journal of Surfactants and Detergents, 2012, 15 (5) : 657-661. doi: 10.1007/s11743-012-1359-7
[25]	Rosen M J, Kunjappu J T. Surfactants and interfacial phenomena[M]. John Wiley & Sons, 2012.

Samples	V₀/mL	V₁/mL
DMOA	0.47	0.07
DMOA（CO₂）	3.80	1.67
DMOA（N₂）	0.97	0.67
DMOA-SOX	0.33	0.03
DMOA-SOX（CO₂）	1.10	0.83
DMOA-SOX（N₂）	0.43	0.13