超高效液相色谱法快速测定化妆品中23种防腐剂

doi:10.3969/j.issn.1001-1803.2022.10.014

摘要/Abstract

摘要：

采用超高效液相色谱法,建立同时测定化妆品中23种防腐剂的快速分析方法。样品用甲醇提取,经CAPCELL CORE C₁₈（2.1 mm×150 mm,2.7 μm）色谱柱分离,流动相为0.1%磷酸-乙腈,梯度洗脱,流速为0.4 mL/min,检测波长为280,254及230 nm。分析结果表明,该方法的方法学验证结果良好,分离效果好,分析时间短,操作简便,流动相组成简单,可用于日常化妆品中防腐剂的快速检测。

关键词: 化妆品, 防腐剂, 超高效液相色谱, 快速分析

Abstract:

A rapid analytical method for the simultaneous determination of 23 preservatives in cosmetics was established by ultra-high performance liquid chromatography （UPLC）. The sample was extracted with methanol and separated by CAPCELL CORE C₁₈ column （2.1 mm×150 mm, 2.7 μm） chromatographic column separation using 0.1% phosphoric acid acetonitrile as the mobile phase with gradient elution. The flow rate was 0.4 mL/min, and the detection wavelength was 280, 254 and 230 nm. The results show that the method has good methodological validation, good separation effect, short analysis time, simple operation and simple composition of mobile phase, which can be used for rapid detection of preservatives in daily cosmetics.

Key words: cosmetics, preservative, ultra performance liquid chromatography, rapid analysis

中图分类号:

TQ658

张伟清,刘慧锦,王海燕,孙磊. 超高效液相色谱法快速测定化妆品中23种防腐剂[J]. 日用化学工业（中英文）, 2022, 52(10): 1128-1134.

Zhang Weiqing,Liu Huijin,Wang Haiyan,Sun Lei. Rapid determination of 23 preservatives in cosmetics by ultra performance liquid chromatography[J]. China Surfactant Detergent & Cosmetics, 2022, 52(10): 1128-1134.

图/表 6

表1

表2

图1

表3

表4

23种防腐剂的回收率和精密度"

组分	添加量/（μg/mL）	膏霜		油基		香波
组分	添加量/（μg/mL）	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
甲基异噻唑啉酮	0.1	108.3	3.93	106.4	4.52	110.2	3.94
	0.2	119.4	3.25	110.9	4.76	113.3	4.02
	0.4	110.9	4.16	107.7	4.32	109.7	3.83
2-溴-2硝基丙烷-1,3二醇	3.75	107.5	2.13	103.5	2.54	111.9	3.23
	7.5	110.9	2.52	111.5	4.26	109.9	3.30
	15	114.7	4.95	107.6	4.28	102.0	4.20
4-羟基苯甲酸	0.5	117.6	3.01	112.3	4.27	112.4	3.43
	1	117.4	2.35	113.1	3.97	113.5	2.83
	2	113.5	3.59	108.5	3.72	111.7	2.72
甲基氯异噻唑啉酮	0.1	114.4	2.41	104.3	3.73	101.8	3.69
	0.2	107.5	2.96	106.9	4.05	107.4	3.70
	0.4	110.2	1.86	106.0	2.35	109.5	3.64
苯甲醇	7.5	113.3	2.33	110.4	3.63	119.9	3.71
	15	113.2	3.25	109.5	2.48	109.7	2.35
	30	110.3	1.29	106.8	2.33	110.0	3.05
苯氧乙醇	5	115.3	1.96	112.0	1.97	114.5	2.38
	10	115.3	2.45	110.9	3.43	110.1	2.05
	20	110.1	2.33	106.6	1.21	108.8	2.13
苯甲酸	1.25	112.1	3.17	104.0	4.05	107.1	3.13
	2.5	115.7	2.84	107.3	3.96	107.5	2.99
	5	111.4	2.73	107.2	3.75	110.2	3.70
4-羟基苯甲酸甲酯	0.312 5	88.2	3.89	85.7	4.45	87.1	3.49
	0.625	105.8	4.30	99.4	3.26	104.0	3.05
	1.25	121.2	3.47	100.8	3.08	111.2	2.30
氯苯甘醚	0.75	101.6	2.82	92.4	3.06	99.7	3.30
	1.5	109.2	1.96	105.9	2.98	105.3	2.24
	3	104.0	1.88	102.2	2.64	104.6	3.20
脱氢乙酸	0.75	101.4	1.98	105.3	2.99	105.1	2.34
	1.5	109.5	1.75	106.4	3.35	106.6	4.01
	3	105.5	3.06	102.2	4.53	104.3	4.35
5-溴-5-硝基-1,3-二噁烷	6.25	114.7	2.99	110.9	3.28	113.5	4.35
	12.5	115.1	3.53	111.0	3.43	110.8	3.95
	25	111.0	3.61	106.3	3.62	109.3	3.78
4-羟基苯甲酸乙酯	0.625	110.8	2.82	107.0	3.48	108.7	2.67
	1.25	105.0	2.05	101.0	3.23	100.8	3.06
	2.5	108.0	3.40	103.7	3.61	103.9	3.83
4-羟基苯甲酸异丙酯	0.625	110.6	2.68	107.1	3.85	107.3	4.06
	1.25	114.9	4.02	107.2	4.24	108.2	4.13
	2.5	108.4	3.64	103.7	3.98	106.3	3.25
4-羟基苯甲酸丙酯	0.625	104.6	4.05	96.7	4.67	108.1	4.06
	1.25	104.1	3.88	110.9	4.36	99.2	3.97
	2.5	113.9	4.42	93.5	4.25	108.5	4.28
4-羟基苯甲酸苯酯	0.75	113.8	3.75	110.6	3.68	110.1	3.12
	1.5	113.9	2.99	109.3	2.98	110.2	3.20
	3	109.1	3.74	104.1	2.74	106.9	3.23
4-羟基苯甲酸异丁酯	0.75	110.0	2.99	104.9	3.15	105.3	3.24
	1.5	111.2	3.62	106.6	2.98	106.9	3.75
	3	107.4	3.73	102.2	2.77	105.1	2.98
4-羟基苯甲酸丁酯	0.75	119.6	4.32	114.6	2.94	115.6	3.63
	1.5	116.6	4.05	112.2	4.00	114.0	3.58
	3	109.1	4.58	103.4	3.68	105.9	4.54
4-羟基苯甲酸苄酯	0.75	98.4	2.01	89.7	3.74	85.7	3.76
	1.5	92.6	3.60	88.6	2.86	90.7	2.82
	3	89.8	2.66	89.9	1.45	90.2	4.76
苯甲酸乙酯	1.5	109.8	2.23	104.9	2.76	104.7	4.05
	3	110.5	2.81	105.8	3.10	105.9	4.10
	6	106.1	3.81	101.7	2.83	104.2	4.28
4-羟基苯甲酸戊酯	1.5	109.0	2.05	105.5	2.24	104.1	2.75
	3	110.2	3.62	105.0	3.33	105.7	2.86
	6	105.4	3.83	100.1	4.05	103.4	3.64
苯甲酸异丙酯	1.75	100.0	3.75	97.4	2.98	94.9	3.45
	3.5	102.5	2.20	96.9	2.67	97.1	3.05
	7	95.9	1.24	92.2	2.34	96.2	2.56
苯甲酸丙酯	1.75	94.2	1.53	93.3	3.87	87.3	2.93
	3.5	100.6	2.05	93.7	2.75	94.8	2.73
	7	93.9	1.60	91.0	2.07	94.0	2.35
苯甲酸苯基酯	2	91.6	4.30	90.2	3.43	93.7	4.05
	4	119.7	2.98	110.5	4.12	114.8	3.68
	8	105.5	3.99	96.3	4.05	103.6	3.49

表4

表5

参考文献 17

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组分	线性方程	R²	线性范围/ （mg/L）	检出限/ng	定量限/ng
甲基异噻唑啉酮	y=16 415.6x+51.3	0.999 9	0.04~4.00	3	9
2-溴-2硝基丙烷-1,3二醇	y=74.6x-15.76	0.999 9	1.50~750.00	346	1 154
4-羟基苯甲酸	y=8 082.7x-579.0	0.999 9	0.20~100.00	6	19
甲基氯异噻唑啉酮	y=11 519.0x-206.5	0.999 9	0.04~20.00	4	13
苯甲醇	y=411.8x-442.9	0.999 9	3.00~1 500.00	120	400
苯氧乙醇	y=1 103.4x+2 384.7	0.999 9	2.00~1 000.00	48	158
苯甲酸	y=1 751.1x-999.4	0.999 9	0.50~250.00	34	112
4-羟基苯甲酸甲酯	y=8 599.5x-335.2	0.999 9	0.12~62.50	7	24
氯苯甘醚	y=790.0x+331.9	0.999 8	0.30~150.00	88	293
脱氢乙酸	y=6 667.3x-1 791.9	0.999 9	0.30~150.00	10	33
5-溴-5-硝基-1,3-二噁烷	y=262.4x-255.8	0.999 9	2.50~1 250.00	224	746
4-羟基苯甲酸乙酯	y=7 877.6x+2.9	0.999 9	0.25~125.00	8	27
4-羟基苯甲酸异丙酯	y=6 257.5x+87.4	0.999 9	0.25~125.00	9	31
4-羟基苯甲酸丙酯	y=5 564.2x-122.1	0.999 9	0.25~125.00	10	34
4-羟基苯甲酸苯酯	y=13 137.0x-815.3	0.999 9	0.30~150.00	6	18
4-羟基苯甲酸异丁酯	y=5 864.2x-279.9	0.999 9	0.30~150.00	13	43
4-羟基苯甲酸丁酯	y=4 808.8x-344.3	0.999 9	0.30~150.00	16	53
4-羟基苯甲酸苄酯	y=2 058.2x-1 055.2	0.999 9	0.30~150.00	46	153
苯甲酸乙酯	y=3 237.2x-1 022.2	0.999 9	0.60~300.00	27	90
4-羟基苯甲酸戊酯	y=5 019.1x-677.3	0.999 8	0.60~300.00	19	63
苯甲酸异丙酯	y=1 006.8x-1 566.5	0.999 8	0.70~350.00	113	377
苯甲酸丙酯	y=1 141.1x-1 633.5	0.999 9	0.70~350.00	89	297
苯甲酸苯基酯	y=1 680.0x+3 610.4	0.999 6	0.80~400.00	35	115

样品/组分	检测结果/（μg/g）
样品/组分	**牌沐浴露	**牌泡泡沐浴露	**牌护臀膏	**牌维E面霜	**牌维E润肤乳	**牌护肤油	**牌止痒膏
苯氧乙醇	nd	nd	3 721.83	4 013.30	2 308.97	2 004.83	nd
4-羟基苯甲酸甲酯	nd	nd	nd	845.42	1 382.96	1 023.74	nd
4-羟基苯甲酸乙酯	nd	nd	nd	nd	364.98	317.44	nd