气相色谱法测定防晒化妆品中14种防晒剂的含量

doi:10.3969/j.issn.1001-1803.2019.02.012

摘要/Abstract

摘要：

采用甲醇超声萃取防晒化妆品中防晒剂,经DB-5MS毛细管色谱柱分离,氢火焰离子化检测器测定,建立了气相色谱法同时测定防晒化妆品中14种防晒剂的检测方法。结果表明：14种防晒剂在0.5~100.0 mg/kg范围内线性关系良好,相关系数（r ²）≥0.999 3;检出限为0.05~0.15 mg/kg,定量限为0.17~0.50 mg/kg;加标回收率为91. 7%~100.1%,相对标准偏差为1.1%~3.1%。该法操作简便、加标回收率高、精密度好、检出限低,可为防晒化妆品中防晒剂的种类和含量测定提供参考。

关键词: 防晒剂, 防晒化妆品, 气相色谱法

Abstract:

A method for simultaneous determination of 14 sunscreen agents in sunscreen cosmetics was established by gas chromatography, with ultrasonic extraction of sunscreen agents in sunscreen cosmetics carried out by DB-5MS capillary column separation and hydrogen flame ionization detector. The results show that the linearity of 14 sunscreen agents is good in the range of 0.5-100.0 mg/kg, and the correlation coefficients are more than 0.999 3. The detection limit is 0.05-0.15 mg/kg, the limit of quantification is 0.17-0.50 mg/kg; the relative standard deviation is 1.1%-3.1%, and the recovery rate of the spiked standards are 91.7%-100.1%. The method has the advantages of simple operation, high recovery rate, good precision and low detection limit, and can provide a detection method for determining the type and content of the sunscreen agent in the sunscreen cosmetic.

Key words: sunscreen agents, sunscreen cosmetics, gas chromatography

中图分类号:

TQ658.2 +4

朱惠斌,王雪平. 气相色谱法测定防晒化妆品中14种防晒剂的含量[J]. 日用化学工业, 2019, 49(2): 126-131.

Hui-bin ZHU,Xue-ping WANG. Determination of 14 sunscreen agents in sunscreen cosmetics by gas chromatography[J]. China Surfactant Detergent & Cosmetics, 2019, 49(2): 126-131.

图/表 7

表 1

图 1

表 2

表 3

表4

回收率和精密度（n=6）"

物质	添加水平/（mg·kg^-1）	回收率/%						平均回收率/%	RSD/%
物质	添加水平/（mg·kg^-1）	1	2	3	4	5	6	平均回收率/%	RSD/%
MOME	0.5	94.1	97.2	93.7	91.9	99.3	90.7	94.5	1.4
	50.0	91.0	97.0	99.5	97.7	91.5	93.7	95.1	1.5
	100.0	95.9	93.2	101.9	95.5	95.9	100.3	97.1	2.1
BP3	0.5	90.5	93.5	95.3	99.7	97.5	93.7	95.0	2.7
	50.0	91.7	90.5	97.7	95.7	93.7	95.3	94.1	2.3
	100.0	99.3	93.7	97.3	97.5	93.8	101.1	97.1	2.8
IPM	0.5	93.5	91.7	93.1	95.3	95.3	99.3	94.7	2.5
	50.0	101.7	93.5	97.3	101.7	99.9	97.3	98.6	2.9
	100.0	98.3	100.7	99.5	93.4	99.7	93.5	97.5	2.3
OTC	0.5	93.1	99.0	99.9	93.7	93.5	93.5	95.5	2.4
	50.0	92.5	95.3	101.3	97.5	93.5	91.1	95.2	1.8
	100.0	93.5	99.7	91.5	94.3	93.8	97.5	95.1	1.3
MOEE	0.5	93.5	93.7	93.5	99.7	95.1	97.3	95.5	1.4
	50.0	95.3	95.1	93.0	90.0	93.9	97.3	94.1	2.0
	100.0	95.7	97.3	100.3	99.9	103.7	95.7	98.8	2.6
ES	0.5	90.3	93.7	91.9	97.1	93.9	93.3	93.4	2.6
	50.0	97.9	99.1	90.5	91.5	97.3	97.5	95.6	3.1
	100.0	103.3	99.3	97.7	103.7	92.5	101.5	99.7	2.4
HS	0.5	99.3	91.3	93.5	95.9	91.3	95.9	94.5	2.5
	50.0	99.9	91.3	99.7	95.3	91.9	93.1	95.2	3.1
	100.0	95.3	93.7	99.3	99.5	91.3	95.7	95.8	1.6
ABA	0.5	93.5	91.7	93.1	95.3	95.3	99.3	94.7	1.9
	50.0	91.3	99.0	93.9	91.9	91.7	97.3	94.2	1.4
	100.0	99.0	95.7	97.5	97.7	91.0	90.0	95.2	1.6
PABA	0.5	99.9	97.9	100.3	101.3	99.5	101.7	100.1	2.5
	50.0	97.3	99.3	93.7	93.3	91.5	93.0	94.7	1.8
	100.0	93.7	91.5	92.1	90.8	89.3	92.5	91.7	1.2
4AP	0.5	93.5	95.0	99.1	97.1	99.5	97.5	96.9	2.1
	50.0	99.7	93.5	95.1	93.5	95.7	93.9	95.2	1.7
	100.0	99.7	100.5	99.0	97.9	103.5	97.7	99.7	1.6
ESC	0.5	99.3	91.3	93.5	95.9	91.3	95.9	94.5	1.5
	50.0	99.9	91.3	99.7	95.3	91.9	93.1	95.2	2.1
	100.0	95.3	93.7	99.3	99.5	91.3	95.7	95.8	2.6
CA	0.5	93.5	91.7	93.1	95.3	95.3	99.3	94.7	1.9
	50.0	91.3	99.0	93.9	91.9	91.7	97.3	94.2	1.4
	100.0	99.9	97.9	100.3	101.3	99.5	91.7	98.4	1.6
SA	0.5	99.0	95.7	97.5	97.7	91.0	90.0	95.2	1.2
	50.0	97.3	99.3	93.7	93.3	91.9	93.0	94.8	1.8
	100.0	92.7	103.5	103.7	97.3	99.3	95.5	98.7	1.2
BPN	0.5	93.5	95.0	99.0	97.0	99.5	97.5	96.9	1.1
	50.0	90.7	93.5	92.1	93.5	95.7	93.9	93.2	1.7
	100.0	93.7	90.5	91.9	97.9	93.5	92.7	93.4	1.6

表4

图 2

表5

参考文献 18

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序号	中文名称	缩写	CAS号	分子式	分子量	沸点/ ℃	保留时间/min
1	4-甲氧基肉桂酸-2-乙基己酯	MOME	5466-77-3	C₁₈H₂₆O₃	290.37	198.9	33.76
2	二苯甲酮-3	BP3	131-57-7	C₁₄H₁₂O₃	228.24	160	20.81
3	甲氧基肉桂酸异戊酯	IPM	71617-10-2	C₁₅H₂₀O₃	248.32	158	17.14
4	奥克立林	OTC	6197-30-4	C₂₄H₂₇NO₂	361.54	218	35.76
5	4-甲氧基肉桂酸异辛酯	MOEE	83834-59-7	C₁₈H₂₆O₃	290.40	198	31.21
6	水杨酸乙基己酯	ES	118-60-5	C₁₅H₂₂O₃	250.33	189	27.33
7	胡莫柳酯	HS	118-56-9	C₁₆H₂₂O₃	262.34	161	24.03
8	对氨基苯甲酸	ABA	150-13-0	C₇H₇NO₂	137.10	251.9	39.21
9	PEG-25对氨基苯甲酸	PABA	113010-52-9	C₇H₇NO₂	357.40	187	26.41
10	对羟基苯甲酮	4AP	1137-42-4	C₁₃H₁₀O₂	198.22	260	41.87
11	2-氰基-3,3-二苯基丙烯酸-2-乙基己酯	ESC	6197-30-4	C₂₄H₂₇NO₂	361.48	218	35.21
12	肉桂酸	CA	621-82-9	C₉H₈O₂	148.16	300	45.67
13	水杨酸苯酯	SA	118-55-8	C₁₃H₁₀O₃	214.23	172	24.91
14	二苯甲酮	BPN	119-61-9	C₁₃H₁₀O	182.22	305	47.43

序号	目标物	线性方程	线性范围/（mg·kg^-1）	相关系数	LOD/（mg·kg^-1）	LOQ/（mg·kg^-1）
1	MOME	y=46.615x+0.217	0.5~100.0	0.999 8	0.12	0.40
2	BP3	y=41.754x+0.281	0.5~100.0	0.999 7	0.12	0.40
3	IPM	y=38.425x+0.239	0.5~100.0	0.999 8	0.15	0.50
4	OTC	y=84.272x+0.109	0.5~100.0	0.999 3	0.08	0.25
5	MOEE	y=125.61x-12.36	0.5~100.0	0.999 7	0.05	0.17
6	ES	y=28.641x+0.216	0.5~100.0	0.999 8	0.15	0.50
7	HS	y=54.617x+0.173	0.5~100.0	0.999 7	0.09	0.30
8	ABA	y=56.645x+0.367	0.5~100.0	0.999 8	0.09	0.30
9	PABA	y=87.524x+0.234	0.5~100.0	0.999 6	0.06	0.20
10	4AP	y=67.526x+0.124	0.5~100.0	0.999 3	0.08	0.25
11	ESC	y=74.413x+0.342	0.5~100.0	0.999 6	0.09	0.30
12	CA	y=59.384x+0.342	0.5~100.0	0.999 4	0.09	0.30
13	SA	y=28.154x+0.214	0.5~100.0	0.999 6	0.15	0.50
14	BPN	y=68.231x+0.137	0.5~100.0	0.999 5	0.09	0.30

分析对象	仪器	防晒剂	回收率/%	RSD/%	检出限/（mg·kg^-1）	参考文献
化妆品	超高效合相色谱仪	7种	90.2~103.0	1.6~5.2	200	[13]
化妆品	液相色谱仪	15种	88.7~108.0	1.6~4.3	01.0~10.0	[15]
化妆品	液相色谱仪	9种	85.7~108.4	1.3~5.1	0.08~100	[16]
化妆品	气相色谱-质谱仪	11种	98.2~101.2	0.3~1.6	0.05~5.0	[17]
防晒化妆品	气相色谱仪	14种	91.7~100.1	1.1~3.1	0.17~0.50	本方法