棕榈酰基蛋氨酸表面活性剂的合成与性能

doi:10.16085/j.issn.1000-6613.2018-0933

摘要/Abstract

摘要：

以天然产物棕榈酸和蛋氨酸为原料，通过酰氯化反应和酰胺化反应两步法合成棕榈酰基蛋氨酸表面活性剂（PMS），探究反应温度、反应时间、反应物摩尔比、反应介质体积比等因素对酰胺化反应的影响；通过傅里叶红外光谱（FTIR）、核磁共振氢谱（¹H NMR）和质谱对产物的结构进行表征；研究产物的表面性能和复配体系的性能。实验结果表明：酰胺化反应最佳反应温度为30℃、n(棕榈酰氯)∶n(蛋氨酸)=1∶1.2、V(水)∶V(丙酮)=1∶2、反应时间为2.5h，在此条件下，得到产物产率89.0%；表征的结果为目标产物；合成产物临界胶束浓度为 1.2×10^-4mol/L，表面张力为29.59mN/m；对苯等有机溶剂的乳化作用明显优于月桂酰基谷氨酸（LAS）；PMS与椰油丙基甜菜碱（CPBS）摩尔比为4∶6时复配体系表面活性最佳，临界胶束浓度达到9.5×10^-5mol/L，复配体系表面张力为28.1mN/m。

关键词: 氨基酸表面活性剂, 棕榈酸, 蛋氨酸, 性能测试, 复配

Abstract:

Palmitoyl methionine surfactant (PMS) was synthesized using natural palmitic acid and methionine by acyl chloride reaction and amidation reaction. The effect of reaction temperature, molar ratio of reactants, reaction medium volume ratio, and reaction time on the amidation reaction was investigated by single factor experiment method. In addition, the structure of the product was characterized by FTIR、¹H NMR and mass spectra, and the surface properties of the product and the properties of the complex system were determined. The results showed that the optimal conditions of amidation reaction were screened out as follows: reaction temperature of 30℃, the molar ratio of reactants 1∶1.2, the volume ratio of reaction medium 1∶2, and the optimum reaction time 2.5h. Under the above conditions, the product yield was 89.0%. And the result of the characterization is the target product. Furthermore, the critical micelle concentration (CMC) and surface tension of product were 1.2×10^-4mol/L and 29.59mN/m, respectively. The emulsification of the product with many organic solvents was clearly superior to lauroyl glutamic acid surfactant(LAS). When the molar ratio of PMS and coconut oil propyl betaine surfactant (CPBS) was 4∶6, the surface properties of the complex system was the best. Under those conditions, the CMC and surface tension of the complex system were 9.5×10^-5mol/L and 28.1mN/m, respectively.

Key words: amino acid surfactant, palmitic acid, methionine, performance test, compounding

中图分类号:

TQ423.11

龚哲, 尚小琴, 杨金婵, 黄文进, 赖心翘, 刘丹彤, 黄炯浩. 棕榈酰基蛋氨酸表面活性剂的合成与性能[J]. 化工进展, 2019, 38(02): 1068-1074.

Zhe GONG, Xiaoqin SHANG, Jinchan YANG, Wenjin HUANG, Xinqiao LAI, Dantong LIU, Jionghao HUANG. Synthesis and properties of palmitoyl methionine surfactant[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 1068-1074.

图/表 13

参考文献 15

1	INFANTEM R, PEREZL, PINAZOA, et al．Amino acid-based surfactants[J]．Comptes Rendus Chimie, 2004, 7(6): 583-592．
2	BORDESR, HOLMBERGK. Amino acid-based surfactants—do they deserve more attention?[J]. Adv. Colloid Interface Sci., 2015, 222: 79-91．
3	汪保川, 李宇鹏, 戴国琛, 等. 蛋白基表面活性剂的合成、性能与应用进展[J]. 化工进展, 2017, 36(7): 2607-2614.
	WANGBaochuan, LIYupeng, DAIGuochen, et al. Synthesis, properties and applications of protein-based surfactants[J]. Chemical Industry and Engineering Progress, 2017, 36(7): 2607-2614.
4	王娟, 王丹, 商士斌, 等. 天然产物基Gemini表面活性剂研究进展[J]. 化工进展, 2012, 31(12): 2761-2765.
	WANGJuan, WANGDan, SHANGShibing, et al. Development of natural product Gemini surfactants[J]. Chemical Industry and Engineering Progress, 2012, 31(12): 2761-2765.
5	SÁNCHEZL, MARTINEZV, INFANTEM R, et al. Hemolysis and antihemolysis induced by amino acid-based surfactants[J]. Toxicology Letters, 2007, 169(2): 177-184.
6	PINHEIROL, FAUSTINOC. Amino acid-based surfactants for biomedical applications[M]//Application and Characterization of Surfactants. London: IntechOpen， 2017.
7	PERINELLID R, CASETTARIL, CESPIM, et al. Chemical-physical properties and cytotoxicity of N-decanoyl amino acid-based surfactants: effect of polar heads[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2016, 492: 38-46.
8	AMPATZIDISC D, VARKAE M A, KARAPANTSIOST D. Interfacial activity of amino acid-based glycerol ether surfactants and their performance in stabilizing O/W cosmetic emulsions[J]. Colloids & Surfaces A: Physicochemical & Engineering Aspects, 2014, 460(9): 176-183.
9	LIANGY, HUZ, CAOD. Surface adsorption and aggregation properties of novel L-lysine-based Gemini surfactants[J]. Journal of Surfactants & Detergents, 2014, 17(4): 693-701.
10	曾哲灵, 王林林, 郑菲, 等. 樟树籽仁油合成癸/月桂酰基谷氨酸钠工艺研究[J]. 中国油脂, 2013, 38(2): 69-72.
	ZENGZheling, WANGlinlin, ZHENGFei, et al. Study on the
	synthesis of decyl/lauroyl glutamate from camphor tree seed oil[J].
	Chinese Oils, 2013, 38(2): 69-72.
11	卢峰, 周侨发. N-月桂酰基-L-谷氨酸钠的合成及性能[J]. 广东化工, 2013, 40(6): 13-14.
	LUFeng, ZHOUQiaofa. Synthesis and properties of N-lauroyl-L-glutamate[J]. Guangdong Chemical Industry, 2013, 40(6): 13-14.
12	陈燕妮, 卢云, 吴昊, 等. N-酰基氨基酸系列表面活性剂的合成和应用[J]. 化学研究与应用, 2001, 13(2): 192-195.
	CHENYanni, LUYun, WUHao, et al. Synthesis and application of N-acyl amino acid series surfactants[J]. Chinese Journal of Chemical Research, 2001, 13(2): 192-195.
13	张逸伟, 饶磊, 徐旭辉, 等. 含亚砜基蛋氨酸型表面活性剂的合成及性能[J]. 精细化工, 2015, 32(11): 1212-1216.
	ZHANGYiwei, RAOlei, XUXuhui, et al. Synthesis and properties of sulfoxide-containing methionine surfactants[J]. Fine Chemicals, 2015, 32(11): 1212-1216.
14	王信锐, 尚小琴, 赖雅平, 等. 棕榈酰胺丙基甜菜碱两性表面活性剂的合成及其性能[J]. 精细化工, 2017, 34(3): 268-273.
	WANGXinrui, SHANGXiaoqin, LAIYaping, et al. Synthesis and properties of palmitamide propyl betaine amphoteric surfactant[J]. Fine Chemicals, 2017, 34(3): 268-273.
15	林璟, 郑成, 黄武欢, 等. 双酯基型有机硅季铵盐表面活性剂性能研究[J]. 广州大学学报(自然科学版）, 2014(4): 43-46.
	LINJing, ZHENGCheng, HUANGWuhuan, et al. Diester-based silicone quaternary ammonium surfactants[J]. Journal of Guangzhou University (Natural Science), 2014(4): 43-46.

成分	质量分数/%	成分	质量分数/%
棕榈酰基蛋氨酸钠	12	苯甲酸钠	0.2
椰油酰胺丙基甜菜碱	18	色泽剂	2
甘油	4	薰衣草香精	适量
保湿剂	4	柠檬酸	适量
增稠剂	0.25	去离子水	余量
NaCl	2

成分	质量分数/%	成分	质量分数/%
棕榈酰基蛋氨酸钠	12	苯甲酸钠	0.2
椰油酰胺丙基甜菜碱	18	色泽剂	2
甘油	4	薰衣草香精	适量
保湿剂	4	柠檬酸	适量
增稠剂	0.25	去离子水	余量
NaCl	2

有机物种类	乳化时间/s
有机物种类	棕榈酰基蛋氨酸	月桂酰基谷氨酸
三氯化碳	445±10	186±4
四氯化碳	294±5	76±2
液体石蜡	483±11	128±3
甲苯	722±9	475±10
苯	1207±15	559±12

有机物种类	乳化时间/s
有机物种类	棕榈酰基蛋氨酸	月桂酰基谷氨酸
三氯化碳	445±10	186±4
四氯化碳	294±5	76±2
液体石蜡	483±11	128±3
甲苯	722±9	475±10
苯	1207±15	559±12

指标名称	指标要求	产品指标
分类	乳化型/非乳化型	乳化型
原料	符合《化妆品卫生规范》及GB/T 22731的要求	符合
色泽	符合规定色泽	符合
香气	符合规定香型	符合，无异味
质感	均匀一致	均匀一致无颗粒感
耐热	(40±1)℃保持24h，恢复至室温后无分层现象	无分层现象
耐寒	(0±2)℃保持24h，恢复至室温后无分层、泛粗、变色现象	分层、泛粗、变色现象
pH(25℃)	4.0～8.5/4.0～11.0	5.6