高效液相色谱法分析化妆品中苯扎氯铵及苄索氯铵

doi:10.3969/j.issn.1001-1803.2022.09.016

摘要/Abstract

摘要：

建立了高效液相色谱法同时测定化妆品中苯扎氯铵及苄索氯铵含量的方法。选用C₈色谱柱对测定结果以苯扎氯铵计的3种二甲基苄基氯化铵的同系物及苄索氯铵进行分离,以甲醇∶0.1 mol/L醋酸铵缓冲溶液（pH=5）为流动相进行等度洗脱,在260 nm波长下经高效液相色谱-二极管阵列检测器同时测定,将《化妆品安全技术规范》（2015年版）中苯扎氯铵的检测方法及劳拉氯铵、苄索氯铵和西他氯铵的检测方法进行优化合并,选用使用范围较广的C₈色谱柱实现4种组分同时分离;以苯扎氯铵计的3种二甲基苄基氯化铵的同系物、苄索氯铵在一定质量浓度范围内线性关系良好,相关系数均大于0.999 9,4种不同类型基质低、中、高3个质量浓度梯度下加样回收率为90%~110%,RSD为0.3%~4.4%（n=9）。该方法操作简单、分析时间短,灵敏度和重现性良好,可运用于化妆品中同时快速检测苯扎氯铵、苄索氯铵。

关键词: 高效液相色谱法, 化妆品, 防腐剂, 苯扎氯铵, 苄索氯铵

Abstract:

A method for simultaneous determination of benzalkonium chloride and benzethonium chloride in cosmetics was established by high performance liquid chromatography. Different types of chromatographic columns and mobile phase conditions were screened. Finally, C₈ column was used to separate benzethonium chloride and three kinds of homologues of dimethyl benzyl ammonium chlorides calculated with benzalkonium chloride. Methanol : 0.1 mol/L ammonium acetate buffer solution （pH=5） was used as the mobile phase for isocratic elution. The results were simultaneously determined by DAD at the wavelength of 260 nm. Compared with the methods recommended in Technical Specification for Safety of Cosmetics （2015 edition）, the detection method of benzalkonium chloride and the detection method of lauralkonium chloride, benzethonium chloride and cetalkonium chloride were optimized and combined. A C₈ column with a wide range of use was selected to achieve the simultaneous separation of the four components. Benzalkonium chloride and benzethonium chloride have good linear relationship in a certain mass concentration range, and the correlation coefficients are greater than 0.999 9. The recoveries were 90%-110% with RSD of 0.3%-4.4% （n=9） at three mass concentration gradients of low, medium and high for four different types of matrixes. This method has the advantages of simple operation, short analysis time, good sensitivity and reproducibility, and can be used for the simultaneous determination of benzalkonium chloride and benzethonium chloride in cosmetics.

Key words: HPLC, cosmetics, preservative, benzalkonium chloride, benzethonium chloride

中图分类号:

TQ658

王启林,韩晓萍,李镇冰,唐启奎. 高效液相色谱法分析化妆品中苯扎氯铵及苄索氯铵[J]. 日用化学工业, 2022, 52(9): 1023-1058.

Wang Qilin,Han Xiaoping,Li Zhenbing,Tang Qikui. Analysis of benzalkonium chloride and benzethonium chloride in cosmetics by HPLC[J]. China Surfactant Detergent & Cosmetics, 2022, 52(9): 1023-1058.

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参考文献 8

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序号	名称	称样量/g	定容体积/mL	ρ/（mg/L）
1	劳拉氯铵	0.011 51	10	1 127.980 0
2	米他氯铵	0.010 83		1 066.755 0
3	西他氯铵	0.010 74		1 024.596 0
4	苄索氯铵	0.011 88		1 140.480 0

序号	ρ/（mg/L）
序号	名称	系列1	系列2	系列3	系列4	系列5	系列6
1	劳拉氯铵	5.639 9	11.279 8	28.199 5	56.399 0	84.598 5	112.798 0
2	米他氯铵	5.333 7	10.667 5	26.668 8	53.337 7	80.006 6	106.675 5
3	西他氯铵	5.122 9	10.245 9	25.614 9	51.229 8	76.844 7	102.459 6
4	苄索氯铵	5.702 4	11.404 8	28.512 0	57.024 0	85.536 0	114.048 0

序号	名称	线性回归方程	相关系数	线性范围/（mg/L）	LOQ/（mg/L）	LOD/（mg/L）
1	劳拉氯铵	y=1 123.69x+99.370 4	0.999 9	5.639 9~112.798 0	0.4	0.1
2	米他氯铵	y=900.229x+672.909	0.999 9	5.333 7~106.675 5	0.5	0.2
3	西他氯铵	y=909.764x+690.049	0.999 9	5.122 9~102.459 6	0.6	0.2
4	苄索氯铵	y=2 490.15x-526.249	0.999 9	5.702 4~114.048 0	0.5	0.2

序号	成分名称	理论加标质量浓度/（mg/L）	水基类		乳液类		膏霜类		沐浴露
序号	成分名称	理论加标质量浓度/（mg/L）	平均值/%	RSD/%	平均值/%	RSD/%	平均值/%	RSD/%	平均值/%	RSD/%
1	劳拉氯铵	11.279 8	102.3	1.9	99.0	0.4	92.7	2.6	98.2	2.1
		56.399 0	96.7	2.1	101.8	1.2	109.7	3.9	115.3	0.9
		112.798 0	100.4	3.2	93.6	2.7	97.9	1.4	95.7	1.2
2	米他氯铵	10.667 6	93.2	0.4	99.2	4.4	94.3	1.5	96.7	0.8
		53.337 8	108.7	2.6	102.1	3.6	98.2	2.1	98.2	1.3
		106.675 5	94.0	3.7	97.5	0.7	99.1	0.9	97.8	2.3
3	西他氯铵	10.246 0	104.1	4.3	95.1	2.3	104.8	3.5	104.3	1.7
		51.229 8	92.8	1.0	108.4	0.2	100.2	0.9	98.2	0.9
		102.459 6	100.3	1.3	97.9	4.1	99.6	1.1	106.3	2.4
4	苄索氯铵	11.404 8	109.3	0.6	92.5	0.8	102.1	2.6	94.9	1.5
		57.024 0	95.2	2.4	96.3	1.1	100.1	0.7	102.3	1.2
		114.048 0	99.1	0.3	98.1	1.7	98.9	0.3	90.5	0.3

序号	名称	标示成分	苯扎氯铵含量/%	标示含量/%
1	滴眼液1号	苯扎氯铵	0.007	0.01
2	滴眼液2号	苯扎氯铵	0.048	0.05