四硅氧烷Gemini咪唑表面活性剂的合成及表面性能

doi:10.7503/cjcu20150207

摘要/Abstract

摘要：

以三甲基氯硅烷、 γ-氯丙基三氯硅烷、 1,4-二氯丁烷和咪唑等为原料合成了一种新型的四硅氧烷Gemini咪唑表面活性剂([Si₄-4-Si₄im]Cl₂), 通过质谱(MS)和核磁共振氢谱(¹H NMR)证明所得产物为目标产物. 通过Wilhelmy板法测得其在25 ℃下的临界胶束浓度(cmc)为0.54 mmol/L, 水溶液的表面张力(γ_cmc)降至18.6 mN/m. 通过电导率法研究了其胶束形成热力学参数(Δ $G m 0 —$ ,Δ $H m 0 —$ 和Δ $S m 0 —$ ), 表明在15~35 ℃下其胶束化过程是自发进行的, 且为熵驱动过程.

关键词: 四硅氧烷Gemini咪唑表面活性剂, 临界胶束浓度, 电导率, 表面张力, 热力学参数

Abstract:

A new siloxane gemini imidazolium surfactant 3,3'-di[γ-tri(trimethylsiloxy)silyl]propylchloride-1,1'-(1,4-butanediyl)-bisimidazole([Si₄-4-Si₄im]Cl₂) was synthesized with chlorotrimethylsilane, γ-chloropropyltrichlorosilane, 1,4-dichlorobutane and imidazole. The structure of the surfactant was characte-rized by MS and ¹H NMR spectra, and the results proved that it was consistent with the target structure. The surface tension of the surfactant was measured by Wilhelmy measuring plate method at 25 ℃. It indicates that the γ_cmcof the surfactant in aqueous solution can be reduced to 18.6 mN/m and the value of cmc is 0.54 mmol/L. The thermodynamic parameters of micellization(Δ $G m 0 —$ ,Δ $H m 0 —$ ,Δ $S m 0 —$ ) of the surfactant were researched by determination of the electrical conductivity in different concentrations. The results suggest that the process of micellization is spontaneous and micellization of [Si₄-4-Si₄im]Cl₂ is entropydriven at 15—35 ℃.

Key words: Siloxane Gemini imidazolium surfactant, Critical micelle concentration, Electrical conductivity, Surface tension, Thermodynamic parameter

中图分类号:

O647.2

TrendMD:

梁维平, 赵晓辉, 安东, 徐乾, 叶志文. 四硅氧烷Gemini咪唑表面活性剂的合成及表面性能. 高等学校化学学报, 2015, 36(10): 2009.

LIANG Weiping, ZHAO Xiaohui, AN Dong, XU Qian, YE Zhiwen. Synthesis and Surface Properties of Siloxane Gemini Imidazolium Surfactant^†. Chem. J. Chinese Universities, 2015, 36(10): 2009.

图/表 7

Synthetic routes of [Si4-4-Si4im]Cl2

Fig.1 1H NMR spectrum of [Si4-4-Si4im]Cl2 in CDCl3

Fig.2 Surface tension of [Si4-4-Si4im]Cl2(a), [C14-4-C14im]Cl2(b) and [Si4mim]Cl(c) in aqueous solution as a function of concentration at 25 ℃

Table 1 Adsorption parameters of the surfactants in aqueous solution at 298.15 K

Surfactant	cmc/(mmol·L^-1)	γ_cmc/(mN·m^-1)	π_cmc/(mN·m^-1)	Г_max/(μmol·m^-2)	pc₂₀	A_min/nm²
[Si₄-4-Si₄im]Cl₂	0.54	18.6	53.4	0.704	6.04	2.36
[C₁₄-4-C₁₄im]Cl₂	0.27	39.5	32.5	0.811	4.47	2.05
[Si₄mim]Cl^[5]	7.4	20.4	52.1	0.84	5.43	1.98

Fig.3 Specific conductivity as a function of concentration at different temperatures(A) [Si4-4-Si4im]Cl2; (B) [C14-4-C14im]Cl2. Temperature/℃: a. 15; b. 20; c. 25; d. 30; e. 35.

Fig.4 Function diagram of lnXcmc as the absolute temperature T for [Si4-4-Si4im]Cl2(A) and [C14-4-C14im]Cl2(B)

Table 2 Influence of temperature on the parameters of micellization for the surfactants in aqueous solution

Surfactant	T/K	cmc/(mmol·L^-1)	β	Δ $G m 0 —$ /(kJ·mol^-1)	Δ $H m 0 —$ /(kJ·mol^-1)	TΔ $S m 0 —$ /(kJ·mol^-1)
[Si₄-4-Si₄im]Cl₂	288.15	0.533	0.378	-24.30	-2.690	21.610
	293.15	0.547	0.378	-24.67	-2.785	21.885
	298.15	0.557	0.373	-24.89	-2.862	22.028
	303.15	0.570	0.369	-25.16	-2.949	22.211
	308.15	0.580	0.358	-25.21	-3.008	22.202
[C₁₄-4-C₁₄im]Cl₂	288.15	0.265	0.609	-32.56	-4.571	27.989
	293.15	0.273	0.614	-33.17	-4.750	28.420
	298.15	0.281	0.602	-33.31	-4.862	28.448
	303.15	0.282	0.588	-33.42	-4.963	28.457
	308.15	0.297	0.588	-33.82	-5.127	28.693
[Si₄mim]Cl^[5]	288.15	6.6	0.32	-28.64	-40.48	-11.84
	293.15	6.9	0.30	-28.42	-44.39	-15.97
	298.15	7.5	0.27	-28.11	-48.17	-20.06
	303.15	8.2	0.25	-27.71	-51.82	-24.11
	308.15	9.0	0.22	-27.32	-55.35	-28.03

Table 2 Influence of temperature on the parameters of micellization for the surfactants in aqueous solution

Surfactant	T/K	cmc/(mmol·L^-1)	β	Δ $G m 0 —$ /(kJ·mol^-1)	Δ $H m 0 —$ /(kJ·mol^-1)	TΔ $S m 0 —$ /(kJ·mol^-1)
[Si₄-4-Si₄im]Cl₂	288.15	0.533	0.378	-24.30	-2.690	21.610
	293.15	0.547	0.378	-24.67	-2.785	21.885
	298.15	0.557	0.373	-24.89	-2.862	22.028
	303.15	0.570	0.369	-25.16	-2.949	22.211
	308.15	0.580	0.358	-25.21	-3.008	22.202
[C₁₄-4-C₁₄im]Cl₂	288.15	0.265	0.609	-32.56	-4.571	27.989
	293.15	0.273	0.614	-33.17	-4.750	28.420
	298.15	0.281	0.602	-33.31	-4.862	28.448
	303.15	0.282	0.588	-33.42	-4.963	28.457
	308.15	0.297	0.588	-33.82	-5.127	28.693
[Si₄mim]Cl^[5]	288.15	6.6	0.32	-28.64	-40.48	-11.84
	293.15	6.9	0.30	-28.42	-44.39	-15.97
	298.15	7.5	0.27	-28.11	-48.17	-20.06
	303.15	8.2	0.25	-27.71	-51.82	-24.11
	308.15	9.0	0.22	-27.32	-55.35	-28.03

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