CN104345096B - Method for rapidly detecting polyols in cosmetic - Google Patents

Method for rapidly detecting polyols in cosmetic Download PDF

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CN104345096B
CN104345096B CN201310325769.6A CN201310325769A CN104345096B CN 104345096 B CN104345096 B CN 104345096B CN 201310325769 A CN201310325769 A CN 201310325769A CN 104345096 B CN104345096 B CN 104345096B
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solution
cosmetic
sample
standard
cosmetics
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CN104345096A (en
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姚宁
吴玉洁
秦优
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Shanghai Natural Hall Group Co ltd
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JALA CORP
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Abstract

The invention provides a method for rapidly detecting polyols in a cosmetic. The method includes the following steps: using an internal standard solution and a standard substance to prepare a mixed standard solution with different concentrations; preparing a cosmetic sample dispersion, carrying ultrasonic extraction, filtering, and placing the obtained filtrate put in a closed container to obtain a cosmetic sample solution for later use; respectively carrying out gas chromatographic analysis on the mixed standard solution and the cosmetic sample solution; and using an internal standard technology to draw a standard in order to obtain the concentrations and the content of alcohol components. The method has the advantages of simple operation, high efficiency and reliable result, and can be used to simultaneously quantitatively detect 8 polyols in the cosmetic.

Description

The method for quick of polyalcohols in a kind of cosmetics
Technical field
The invention belongs to cosmetic composition analysis detection field, the quick inspection of polyalcohols in more particularly, to a kind of cosmetics Survey method.
Background technology
In cosmetics, chemical composition is varied, and alcohols is widely used raw material in cosmetics industry, wetting agent and steady Determine agent.In cosmetics, " polyhydric alcohol " class wetting agent mainly includes butanediol, Polyethylene Glycol, propylene glycol, ethylene glycol, glycerol etc..Though So polyalcohols wetting agent has good moistening effect, but is excessively used some polyhydric alcohol and has potential danger.Research shows, The propylene glycol of high concentration and ethylene glycol expose, and can interefere seriously with health.Low dose of or micro propylene glycol and being used for of butanediol Be typically considered safe in cosmetic and food, but be as propylene glycol and butanediol accumulate in the body also can cause lung, Heart and central nervous system injury.2009 2 months, European Union formally issued in new cosmetics instruction and explicitly points out in cosmetics Diethylene glycol mass fraction must not exceed 0.1%.
Because different alcohols structural properties are not quite similar, the sample substrate being additionally present of is also complicated various, therefore, existing mark For different alcohols wetting agents in standard, use the detection meanss in different State of cosmetics different.At present, detect alcohol The standard species of class is various, and the experiment condition being related to is also different.The alcohols wetting agent species that prior art is directed to detection compares Single, tend not to the multiple common alcoholic of one-time detection.Detect all of alcohols, then need repeated detection, cause detection week Phase lengthens, and reduces efficiency.Therefore, existing detection method cannot meet the detection demand for alcohols in cosmetics for the market.
Content of the invention
It is an object of the invention to:There is provided a kind of method for quick of polyalcohols in cosmetics it is intended to meet market Detection demand for alcohols in cosmetics.
The object of the present invention is achieved like this:
In a kind of cosmetics, the method for quick of polyalcohols, comprises the following steps:
Make the mixed standard solution of variable concentrations with inner mark solution and standard substance;
Prepared by cosmetic sample solution:Preparing cosmetics sample dispersion liquid, supersound extraction, filtration, filtrate is placed in airtight In container, obtain cosmetic sample solution, stand-by;
Gas chromatographic analysiss are carried out respectively to described mixed standard solution and cosmetic sample solution;
Draw standard curve with internal standard method and draw the concentration of alcohol component and alcohol content in sample solution.
The present invention rapidly and accurately can detect the polyhydric alcohol of 1-8 kind and its quantitation in cosmetics simultaneously, also has behaviour Make the advantages of easy, anti-matrix interference, reliable results, and this method also extend to many in similar system (as food) First alcohol and other low boiling alcohols (ethanol, isopropanol, hexadecanol, octadecanol etc.).
Brief description
Fig. 1 is the chromatogram of alcohols standard substance;
Fig. 2 is the chromatogram of cosmetic sample A (eye cream);
Fig. 3 is the chromatogram of cosmetic sample B (facial cream);
Fig. 4 is the chromatogram of cosmetic sample C (cosmetic water);
Fig. 5 is the chromatogram of cosmetic sample D (facial cream).
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and It is not used in the restriction present invention.
The various chemical raw materials that the present invention refers to, instrument and equipment all can be commercially available by existing approach.Following realities Apply the method in example, if no special instructions, be conventional method.
Embodiment 1:The selection of testing conditions
Gas chromatograph:Agilent 7890 type gas chromatograph, joins flame ionization ditector (FID);
Chromatographic column:HP-INNOWax, specification is:30m × 0.32mm × 0.25 μm or other fixing phase are Polyethylene Glycol Capillary chromatographic column;Analytical balance:Precision 0.1mg;
Solvent:Methanol (chromatographically pure);
Internal standard substance:N-butyl alcohol (analysis pure) or other any have stable response under this chromatographic condition, and polynary with to be measured The different alcohols of alcohol retention;
Standard substance:Ethanol, isopropanol, 1,2-PD, 1,3-PD, 1,3 butylene glycol, 1,2- pentanediol, 1,2- are own Glycol, 1,2- ethohexadiol, dipropylene glycol, glycerol, hexadecanol, octadecanol;
Cosmetic sample:A (eye cream), B (facial cream), C (cosmetic water), D (facial cream).
Embodiment 2:The preparation of standard solution
Above-mentioned internal standard substance and solvent are configured to the inner mark solution of 0.1-50mg/mL (preferably 10mg/mL).
Accurately weigh each about 50mg of above-mentioned various standard substance in same 25mL volumetric flask, carved with methanol constant volume to 25mL Degree, the mixed standard solution of prepared 2mg/mL.
By described mixed standard solution stepwise dilution, and add inner mark solution in the mixed mark solution of every grade of concentration, finally It is configured to the standard solution (concentration range 0.005-2mg/mL) of 2-5 level Concentraton gradient.
Embodiment 3:The preparation of sample solution
Accurately weigh above-mentioned various cosmetic sample respectively in volumetric flask, after adding inner mark solution, with methanol constant volume extremely Volumetric flask scale, is configured to the dispersion liquid in 2-50mg/mL for the sample concentration;After supersound extraction (5-30min), with dried and clean Defecator filters, and filtrate is sample solution, is placed in be measured in the airtight container of cleaning.
Embodiment 4:Polyhydric alcohol in solution is detected by gas chromatography
Gas chromatograph quantitative analyses condition:Take split sampling mode (split ratio 10: 1);Injector temperature 180-220 DEG C (preferably 220 DEG C);Carrier gas is High Purity Nitrogen, flow velocity 1.0mL/min;Sample size 0.1-2 μ L (preferably 1 μ L);Heating schedule:Initially Temperature 40-70 DEG C (preferably 60 DEG C), is raised to 220-240 DEG C (preferably with 2-15 DEG C/min (preferably 10 DEG C/min) after keeping 2min 230 DEG C), keep 5-15min (preferably 10min);250-300 DEG C of detector temperature (preferably 280 DEG C).
Series standard solution and sample solution are detected respectively by gas chromatograph, draws standard curve with internal standard method and obtain Obtain the concentration of the various alcohol component containing in sample solution, and calculate the content of the every kind of alcohol in sample by formula (1):
Formula (1)
Wherein:C0:The concentration (mg/mL) of sample dispersion liquid;
C:The concentration (mg/mL) of this alcohol in sample solution
Embodiment 5:The range of linearity of alcohols and its in cosmetics content corresponding relation
In conjunction with the chromatogram of the alcohols standard substance shown in Fig. 1, the range of linearity of each alcohols standard substance can be obtained and its making up The corresponding relation of content in product, as shown in table 1:
Table 1
Due to content in cosmetics for the polyhydric alcohol wetting agent generally 0.2-10% about, the change of preparation about 10mg/mL The detection that cosmetic sample dispersion liquid can meet polyhydric alcohol wetting agent requires.
Embodiment 6:Polyhydric alcohol detection in cosmetic sample A (eye cream)
The gas chromatogram of cosmetic sample A (eye cream) is as shown in Fig. 2 make mirror for convenience of comparison by mixed standard solution collection of illustrative plates As processing, record in cosmetic sample A (eye cream) and contain 1,3 butylene glycol, the content being computed 1,3 butylene glycol is as shown in table 2:
Table 2
The polyhydric alcohol being added in sample A Addition (%) Measured value (%)
1,3 butylene glycol 5.0 5.2
Embodiment 7:Polyhydric alcohol detection in cosmetic sample B (facial cream)
The gas chromatogram of cosmetic sample B (facial cream) is as shown in figure 3, make mirror for convenience of comparison by mixed standard solution collection of illustrative plates As processing, record and in cosmetic sample B (facial cream), contain 1,3-PD and glycerol, be computed containing of 1,3-PD and glycerol Amount is as shown in table 3:
Table 3
The polyhydric alcohol that sample B is added Addition (%) Measured value (%)
1,3-PD 10 10.3
Glycerol 7.6 7.5
Embodiment 8:Polyhydric alcohol detection in cosmetic sample C (cosmetic water)
The gas chromatogram of cosmetic sample C (cosmetic water) is as shown in figure 4, do mixed standard solution collection of illustrative plates for convenience of comparison Mirror image processing, records and contains 1,3-PD, 1,2- pentanediol, 1,2- ethohexadiol and double third in cosmetic sample C (cosmetic water) Glycol, be computed 1,3-PD, 1,2- pentanediol, 1,2- ethohexadiol and dipropylene glycol content as shown in table 4:
Table 4
The polyhydric alcohol that sample C is added Addition (%) Measured value (%)
1,3-PD 6.5 6.5
1,2- pentanediol 3.0 3.0
1,2- ethohexadiol 0.2 0.22
Dipropylene glycol 2.0 1.9
Embodiment 9:Polyhydric alcohol detection in cosmetic sample D (facial cream)
The gas chromatogram of cosmetic sample D (facial cream) is as shown in figure 5, make mirror for convenience of comparison by mixed standard solution collection of illustrative plates As processing, record and in cosmetic sample D (facial cream), contain 1,2-PD, 1,3 butylene glycol, 1,2- pentanediol, 1,3- the third two Alcohol, dipropylene glycol, 1,2- hexanediol, 1,2- ethohexadiol and glycerol, are computed 1,2-PD, 1,3 butylene glycol, 1,2- penta 2 Alcohol, 1,3-PD, dipropylene glycol, 1,2- hexanediol, 1,2- ethohexadiol and glycerol content as shown in table 5:
Table 5
The polyhydric alcohol that sample D is added Addition (%) Measured value (%)
1,2-PD 8 7.2
1,3 butylene glycol 5 4.5
1,2- pentanediol 3 2.7
1,3-PD 6 5.8
Dipropylene glycol 4 3.8
1,2- hexanediol 0.2 0.22
1,2- ethohexadiol 0.1 0.13
Glycerol 4 4.3
From upper table and accompanying drawing, detection method that the present invention provides can detect 1-8 kind polyhydric alcohol and its accurately simultaneously Content, and chromatographic peak favorable reproducibility, sample pre-treatments easy and simple to handle it is easy to carry out.
Alcohols detection method in existing cosmetics, mainly in the majority with colorimetry, spectrophotography and gas chromatography, and adopt The result measuring alcohol species in cosmetics with gas chromatography is more quick and sensitive, and GC-External Standard method measures alcohol content Shi Wufa avoids the volatilization of alcohols to cause quantitative deviation, for avoid this error is produced to testing result, the present invention takes gas phase Chromatograph internal standard method is analyzed to alcohols.
《Cosmetics health specification》First in cosmetics is defined in (2007 editions) Part III " health chemical testing method " The assay method of alcohol content, the method is gas chromatography.The method measures Determination of methanol in cosmetics content and is only applicable to containing ethanol Or the cosmetics of isopropanol, and sample method is divided into two kinds of the cosmetics containing propellant with without propellant, sampling method Complexity, samples limited by sample, and cosmetic sample of the present invention sampling is simple, not limited by cosmetic composition or dosage form etc..
When cosmetic sample is processed, prior art requires and carries out multiple dissolving, extraction, mistake to cosmetic sample Filter, still further comprises in some prior arts and carries out heating to cosmetic sample solution and the step such as volatilize, concentrate, these all can Lead to the loss of sample, make testing result inaccurate, and due to usually containing thickening agent, emulsifying agent, powder etc. in cosmetics Material, the extracting solution of cosmetics, especially denseer extracting solution is very easy to when filtering block the duct of filter membrane, leads to filter and is stranded Difficulty, or even sucking filtration dozens of minutes can only leach less than half, and prior art usually requires that leaching all extracting solution just can be carried out The analysis of next step.And the present invention has broken the prejudice that prior art is prepared for cosmetic sample solution, only to cosmetics sample Product are once dissolved, extracted and are filtered, and only need to leach a small amount of filtrate (0.5mL about enough) and can carry out subsequent analysis, filter The amount of liquid enough carries out normal gas chromatographic sample introduction, not only so that operation is more easy, improves efficiency, and decreases The loss of sample, the more preferable testing result simultaneously also obtaining, the type of the polyhydric alcohol that not only can simultaneously detect is more, to every kind of The quantitation of alcohol is also more accurate.Mutually for purposes of the invention, prior art not only complex steps, time-consuming many but also easily lose sample Cause to detect inaccurate.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (2)

1. in a kind of cosmetics the method for quick of polyalcohols it is characterised in that the method comprises the following steps:
Make the mixed standard solution of variable concentrations with inner mark solution and standard substance;
Wherein:Accurately take the ethanol of same components, isopropanol, 1,2-PD, 1,3-PD, 1,3 butylene glycol, 1,2- penta Glycol, 1,2- hexanediol, 1,2- ethohexadiol, dipropylene glycol, glycerol, hexadecanol and octadecanol standard substance in same volumetric flask, With methanol constant volume to volumetric flask scale, obtain mixed standard solution, the concentration range of described mixed standard solution is 0.005-2mg/ mL;
By mixed standard solution stepwise dilution, and it is separately added into inner mark solution, be configured to the mixed standard solution of variable concentrations;
Prepared by cosmetic sample solution:Accurately weigh cosmetic sample in volumetric flask, after adding inner mark solution, use methanol constant volume To scale, it is configured to the sample dispersion liquid that concentration range is 2-50mg/mL, after supersound extraction 5-30min, with the mistake of dried and clean Filter device filters, and filtrate is placed in the airtight container of cleaning, obtains cosmetic sample solution, stand-by;
Described mixed standard solution and cosmetic sample solution are carried out respectively with gas chromatographic analysiss, described gas chromatograph is quantitative Analysis condition be:
Chromatographic column:HP-INNOWax, 30m × 0.32mm × 0.25 μm or other fixing phase are the capillary chromatography of Polyethylene Glycol Post;180-220 DEG C of injector temperature;Carrier gas is High Purity Nitrogen, flow velocity 1.0mL/min;Sample size 0.1-2 μ L;Heating schedule:Initially Temperature 40-70 DEG C, is raised to 220-240 DEG C with 2-15 DEG C/min after keeping 2min, keeps 5-15min;Detector temperature 250-300 ℃;
Draw standard curve with internal standard method and draw the concentration of alcohol component and alcohol content in sample solution.
2. in cosmetics as claimed in claim 1 the method for quick of polyalcohols it is characterised in that described inner mark solution is With n-butyl alcohol or other any have stable response under chromatographic condition, and the alcohols different from polyhydric alcohol retention to be measured is internal standard Thing, methanol is formulated for solvent.
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CN106645536B (en) * 2017-01-09 2018-10-23 宁波职业技术学院 Low molecular weight PEG dressing agent content assaying methods
CN107255685A (en) * 2017-08-01 2017-10-17 厦门鉴科检测技术有限公司 The high performance liquid chromatography of ultraviolet absorber in a kind of detection cosmetics
CN107831131A (en) * 2017-11-13 2018-03-23 龙蟒佰利联集团股份有限公司 A kind of assay method of the polyalcohols organic surface treatment covering amount of titanium dioxide
CN108037231A (en) * 2017-12-13 2018-05-15 中国检验检疫科学研究院 Method that is a kind of while measuring 8 kinds of gylcol ether compounds in cosmetics
CN110954632A (en) * 2019-12-30 2020-04-03 广州艾蓓生物科技有限公司 Method for determining content of 1,2-hexanediol in cosmetics
CN112505164A (en) * 2020-07-10 2021-03-16 中检科(北京)测试技术有限公司 Method for determining propylene glycol, butylene glycol, hexylene glycol, lauryl alcohol, glycerol, stearyl alcohol and cetyl alcohol in cosmetics
CN112268964A (en) * 2020-09-28 2021-01-26 江苏集萃新型药物制剂技术研究所有限公司 Method for measuring content of hexadecanol and octadecanol in medicinal preparation

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