可聚型Gemini表面活性剂的制备、表征及其稳定高内相乳液的研究

doi:10.11949/0438-1157.20250144

摘要/Abstract

摘要：

合成了具有不同长度连接链的可聚型阳离子Gemini表面活性剂PC11-n-11（n=2， 4， 6），采用核磁共振波谱仪（¹H NMR）和红外光谱仪（FTIR）对结构进行了表征，研究了连接链长度对PC11-n-11的界面性能、胶束直径分布、润湿性能和高内相乳液（HIPE）稳定性的影响规律。结果表明，制备的PC11-n-11的界面性能明显优于传统表面活性剂（DTAB），且润湿性能强。随着连接链长度的增加，临界胶束浓度（CMC）和最大表面吸附容量（Γ_max）逐渐减小，每个表面活性剂分子所占据的最小面积（A_min）逐渐增大，界面性能更好，形成的胶束直径先增大后减小，对疏水性表面的润湿性也更好。其中PC11-4-11和PC11-6-11对HIPE的稳定性好，以PC11-6-11为稳定剂通过HIPE模板法成功制备了壳聚糖和聚丙烯酰胺复合的多孔聚合物。

关键词: 可聚型, Gemini表面活性剂, 界面性能, 润湿性, 高内相乳液, 多孔聚合物

Abstract:

Firstly, polymerizable cationic Gemini surfactants PC11-n-11(n=2, 4, 6) with different linker chain lengths were synthesized,the structure was characterized by ¹H NMR and FTIR. Secondly, the interfacial properties, micelle diameter distribution, wetting properties and high internal phase emulsion (HIPE) stability of PC11-n-11 were studied. The results demonstrate that the interfacial properties of the prepared PC11-n-11 are significantly superior to those of the conventional surfactant (DTAB), with enhanced wetting performance. As the spacer chain length increases, CMC and Γ_maxgradually decrease, while A_min gradually increases, leading to improved interfacial properties. Among them, PC11-4-11 and PC11-6-11 have good stability to HIPE. The porous polymer composite of chitosan and polyacrylamide was successfully prepared by the HIPE template method using PC11-6-11 as a stabilizer.

Key words: polymerizable, Gemini surfactant, interfacial properties, wettability, high internal phase emulsion, porous polymer

中图分类号:

TQ 317

叶鑫煌, 薛嘉豪, 赵玉来. 可聚型Gemini表面活性剂的制备、表征及其稳定高内相乳液的研究[J]. 化工学报, 2025, 76(8): 4331-4340.

Xinhuang YE, Jiahao XUE, Yulai ZHAO. Synthesis and characterization of polymerizable Gemini surfactants: stabilization of high internal phase emulsion[J]. CIESC Journal, 2025, 76(8): 4331-4340.

图/表 13

图1 PC11-2-11、PC11-4-11和PC11-6-11的合成反应示意图

Fig.1 Schematic diagram of the synthesis reaction of PC11-2-11, PC11-4-11 and PC11-6-11

表1 表面活性剂水溶液在25℃条件下的表面活性参数

Table 1 Surface active of surfactant aqueous solution at 25℃

Surfactants	DTAB^[15]	PC11-2-11	PC11-4-11	PC11-6-11
CMC/(mol·L^-1)	14.72×10^-3	2.71×10^-3	1.46×10^-3	8.70×10^-4
γ_CMC/(mN·m^-1)	38.7	34.5	36.2	37.6
Γ_max/(10^-10 mol·cm^-2)	2.60	1.44	1.28	1.19
A_min/nm²	0.64	1.15	1.30	1.39

图2 多孔聚合物的制备流程

Fig.2 Preparation process of porous polymers

图3 11-溴甲基丙烯酸十一酯(a), PC11-2-11 (b), PC11-4-11 (c), PC11-6-11 (d)的1H NMR谱图

Fig.3 1H NMR spectra of 11-bromomethyl acrylate(a), PC11-2-11 (b), PC11-4-11 (c) and PC11-6-11 (d)

图4 PC11-n-11的FTIR谱图

Fig.4 FTIR spectrum of PC11-n-11

图5 25℃下表面活性剂水溶液的γ-lgC 曲线

Fig.5 γ-lgC curves of surfactant aqueous solutions at 25℃

图6 不同浓度下胶束尺寸

Fig.6 Sizes of micelles at different concentrations

图7 表面活性剂浓度对PTFE表面接触角的影响

Fig.7 Effect of surfactant concentration on contact angle of PTFE surface

图8 不同表面活性剂的水溶液[0.40%(质量)]在 PTFE 上的液滴形状

Fig.8 Droplet shapes of different surfactants[0.40%(mass)] on PTFE

图9 静置0.5 h、5 h、5 d、15 d乳液分层情况[乳化剂浓度为0.3%(质量)]

Fig.9 Emulsion stratification conditions after standing for 0.5 h, 5 h, 5 d and 15 d, respectively[emulsifiers concentration: 0.3%(mass)]

图10 高内相乳液在50℃下加热24 h前[(a) ~ (d)]和后[(e) ~ (h)]的微观形态的显微镜照片[乳化剂浓度为0.3%(质量)]

Fig.10 Microscopic photos of microscopic appearance of high internal phase emulsion before [(a) — (d)] and after [(e) — (h)] heating at 50℃ for 24 h[emulsifiers concentration: 0.3%(mass)]

图11 不同乳化剂添加量的SEM图

Fig.11 SEM images of different emulsifier addition amounts

图12 PC11-6-11和不同乳化剂类型或添加量制备的PolyHIPEs的FTIR谱图

Fig.12 FTIR spectrum of PC11-6-11 and PolyHIPEs prepared with different types or emulsifier dosages

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