羧酸盐双子表面活性剂的合成及性能

doi:10.11944/j.issn.1000-0518.2020.03.190242

摘要/Abstract

摘要：

为筛选环境友好的新型双子表面活性剂,以水杨酸为原料设计合成了5个羧酸盐型双子表面活性剂EODPN1-EODPN5[2,2'-(1,2-CH₂CH₂-二-O-)-二-(4-C_nH₂_n₊₁COPhCOONa),n=5,7,9,11和13],并通过核磁共振波谱仪(NMR)和傅里叶变换红外光谱仪(FT-IR)等对目标产物进行了结构表征。探究了EODPN作为表面活性剂的性能,并利用Gibbs表面吸附方程,通过理论计算得到相关热力学参数,结果表明,目标分子具有优异的表面活性,临界胶束浓度(CMC)值低(最低达0.4 mmol/L),表面张力性能优良(最低达29.74 mN/m),单位面积表面吸附量(Γ)高(最高达3.37×10^-6mol/m²)。通过改变疏水基烷基碳链的长度,优化了EODPN的表面活性和自组装能力,筛选出EODPN4为最佳的表面活性剂。借助EODPN4能与铜离子稳定结合,实现了表面活性剂含量的检测。

关键词: 双子表面活性剂, 羧酸盐, 热力学参数, 表面活性

Abstract:

To screen environmental friendly new gemini surfactants, five carboxylate-type gemini surfactants EODPN1-EODPN 5 [2,2'-(1,2-CH₂CH₂-di-O-)-di-(4-C_nH₂_n₊₁COPhCOONa), n=5, 7, 9, 11 and 13] were synthesized from salicylic acid. The structures of the target products were confirmed by nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FT-IR) spectrometer. The properties of EODPN as surfactants were explored, and the relevant thermodynamic parameters were obtained by theoretical calculation using the Gibbs surface adsorption equation. The results show that EODPN has excellent surface activities, extremely low critical micelle concentration (CMC) values (minimum 0.4 mmol/L), good surface tension reduction performance (minimum 29.74 mN/m) and high surface adsorption per unit area Γ(up to 3.37×10^-6 mol/m²). By changing the length of the hydrophobic alkyl carbon chain, the surface activity and self-assembly ability of EODPN were optimized, and EODPN4 was selected as the best surfactant. Based on EODPN4 which can be stably combined with copper ions, the detection of surfactant content is realized.

Key words: gemini surfactant, carboxylate, thermodynamic parameters, surface activity

张成路, 宋府璐, 周龙, 韩珍, 白茹, 杨帆, 王楠, 孙越冬. 羧酸盐双子表面活性剂的合成及性能[J]. 应用化学, 2020, 37(3): 271-279.

ZHANG Chenglu, SONG Fulu, ZHOU Long, HAN Zhen, BAI Ru, YANG Fan, WANG Nan, SUN Yuedong. Synthesis and Properties of Carboxylate Gemini Surfactants[J]. Chinese Journal of Applied Chemistry, 2020, 37(3): 271-279.

参考文献

[1]	Shamsi S A,Akbay C,Warner I M,et al. Polymeric Anionic Surfactant for Electrokinetic Chromatography:Separation of 16 Priority Polycyclic Aromatic Hydrocarbon Pollutants[J]. Anal Chem,1998,70(14):3078-3083.
[2]	LIU Jiajia,XIE Yicheng,XU Hujun,et al. Synthesis and Properties of a Cationic Gemini Asphalt Emulsifier[J]. Chinese J Appl Chem,2018,35(5):552-558(in Chinese). 刘佳佳,谢益诚,许虎君,等. 一种阳离子Gemini型沥青乳化剂的合成及性能[J]. 应用化学,2018,35(5):552-558.
[3]	Ngimhuang J,Furukawa J,Satoh T,et al. Synthesis of a Novel Polymeric Surfactant by Reductive N-Alkylation of Chitosan with 3-O-Dodecyl-D-glucose[J]. Polymer,2004,45(3):837-841.
[4]	Gao C L,Whitcombe M J,Vulfson E N.Enzymatic Synthesis of Dimeric and Trimeric Sugar-Fatty Acid Esters[J]. Enzyme Microb Technol,1999,25(3/5):264-270.
[5]	Kumar R S,Arunachalam S. Synthesis, Micellar Properties, DNA Binding and Antimicrobial Studies of Some Surfactant-Cobalt(Ⅲ) Complexes[J]. Biophys Chem,2008,136(2/3):136-144.
[6]	Yu D,Wang Y,Zhang J,et al. Effects of Calcium Ions on Solubility and Aggregation Behavior of an Anionic Sulfonate Gemini Surfactant in Aqueous Solutions[J]. J Colloid Interface Sci,2012,381(1):83-88.
[7]	Sakai K,Umezawa S,Tamura M,et al. Adsorption and Micellization Behavior of Novel Gluconamide-Type Gemini Surfactants[J]. J Colloid Interface Sci,2008,318(2):440-448.
[8]	Fitzgerald P A,Carr M W,Davey T W,et al. Preparation and Dilute Solution Properties of Model Gemini Nonionic Surfactants[J]. J Colloid Interface Sci,2004,275(2):649-658.
[9]	Huang X,Han Y C,Wang Y X.Aggregation Properties of Cationic Gemini Surfactants with Dihydroxyethylamino Headgroups in Aqueous Solution[J]. Colloid Surf A,2008,325(1/2):26-32.
[10]	Li R Q,Wei L B,Hu C C,et al. Aggregation Properties of a Novel Class of Amphiphilic Cationic Polyelectrolytes Containing Gemini Surfactant Segments[J]. J Phys Chem B,2010,114(39):12448-12454.
[11]	Asefi D,Mahmoodi N M,Arami M.Effect of Nonionic Co-Surfactants on Corrosion Inhibition Effect of Cationic Gemini Surfactant[J]. Colloid Surf A,2010,355(1/3):183-186.
[12]	Hellberg P E,Bergström K,Holmberg K.Cleavable Surfactants[J]. J Surfactants Deterg,2000,3(1):81-91.
[13]	Ding M M,Li J H,Fu X T,et al. Synthesis, Degradation, and Cytotoxicity of Multiblock Poly(ε-caprolactone urethane)s Containing Gemini Quaternary Ammonium Cationic Groups[J]. Biomacromolecules,2009,10(10):2857-2865.
[14]	Tehrani-Bagha A R, Oskarsson H, Van Ginkel C G. Cationic Ester-Containing Gemini Surfactants: Chemical Hydrolysis and Biodegradation[J]. J Colloid Interface Sci,2007,312(2):444-452.
[15]	Li H B,Wang X Q.Single Quantum Dot-Micelles Coated with Gemini Surfactant for Selective Recognition of a Cation and an Anion in Aqueous Solutions[J]. Sens Actuators B-Chem,2008,134(1):238-244.
[16]	Bagha A R T,Bahrami H,Movassagh B,et al. Interactions of Gemini Cationic Surfactants with Anionic Azo Dyes and Their Inhibited Effects on Dyeability of Cotton Fabric[J]. Dyes Pigm,2007,72(3):331-338.
[17]	Chen F Y,Liu M S,Du J,et al. Preparation and Properties of Novel Asymmetric Gemini Alkyl olyglycosides[J]. Tenside Surfactants Deterg,2015,27(6):455-458.
[18]	Quagliotto P,Montoneri E,Tambone F,et al. Chemicals from Wastes: Compost-Derived Humic Acid-Like Matter as Surfactant[J]. Environ Sci Technol,2006,40(5):1686-1692.
[19]	Acharya D P,Gutiérrez J M,Aramaki K,et al. Interfacial Properties and Foam Stability Effect of Novel Gemini-Type Surfactants in Aqueous Solutions[J]. J Colloid Interface Sci,2005,291(1):236-243.
[20]	Liu J Y,Zhao J X,He Y J.Aggregation of Carboxylate Gemini Surfactant with P-Oxybenzene Spacer in Aqueous Solution Studied by Intrinsic Probe Spectroscopy[J]. Colloid Surf A,2007,304(1/3):25-30.
[21]	Renouf P,Hebrault D,Desmurs J R,et al. Synthesis and Surface-Active Properties of a Series of New Anionic Gemini Compounds[J]. Chem Phys Lipids,1999,99(1):21-32.
[22]	Jiang R,Huang Y X,Zhao J X,et al. Aqueous Two-Phase System of an Anionic Gemini Surfactant and a Eationic Conventional Surfactant Mixture[J]. Fluid Phase Equilib,2009,277(2):114-120.
[23]	Jiang R,Zhao J X,Ma Y H.Dynamic Adsorption of Opposite-Charged Gemini Surfactant Mixture at Air/Water Interface[J]. Colloid Surf A,2006,289(1/3):233-236.
[24]	Gautam A,Kambo N,Upadhyay S K,et al. Anionic Gemini Surfactant Viz. Sodium Salt of Bis(1-dodecenylsuccinamic acid); Synthesis, Surface Properties and Micellar Effect on Oxidation of Reducing Sugars by Hexacyanoferrate(III)[J]. Colloid Surf A,2008,312(2/3):195-202.
[25]	Ibrahim Y A,Elwahy A H M. Efficient Synthesis of a Rang of Benzo-Substituted Macrocyclic Diamides[J]. Synthesis,1993,5(5):503-508.
[26]	Wu X,Dai C,Fang S,et al. The Effect of Hydroxyl on the Solution Behavior of a Quaternary Ammonium Gemini Surfactant[J]. Phys Chem Chem Phys,2017,19(24):16047-16056.
[27]	LIU Haiyan,GU Daming,LIU Guoyu,et al. Synthesis and Surface Properties of Novel Gemini Imidazole Surfactants[J]. Chem J Chinese Univ,2013,34(2):401-407(in Chinese). 刘海燕,顾大明,刘国宇,等. 新型Gemini咪唑表面活性剂的合成及表面性能[J]. 高等学校化学学报,2013,34(2):401-407.
[28]	Yuan F,Wang T T,Hu H M,et al. Two luminescent d10, Metal Coordination Polymers Assembled from a Semirigid Terpyridyl Carboxylate Ligand with High Selective Detecting of Cu2+, Cr2$O_{7}^{2-}$, and Acetone[J]. J Solid State Chem,2017,251(4):79-89.
[29]	Liu C,Tang B,Zhang S,et al. Photoinduced Electron Transfer Mediated by Coordination Between Carboxyl on Carbon Nanodots and Cu2+ Quenching Photoluminescence[J]. J Phys Chem C,2018,122(6):3662-3668.
[30]	Brunner J,Kraemer R.Copper(II)-Quenched Oligonucleotide Probes for Fluorescent DNA Sensing[J]. J Am Chem Soc,2004,126(42):13626-13627.