Determination of twelve polyols and forbidden substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry

Abstract

The application provides a method for determining twelve polyols and a banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry, comprising: dissolving a sample to be determined by using a solvent to obtain a sample to be determined; dissolving the twelve polyols and the diethylene glycol by using a solvent to obtain a control solution; determining the sample to be determined and the control solution by using a gas chromatography-mass spectrometry method; the chromatographic column is a medium-polarity or weak-polarity chromatographic column; the temperature program is as follows: the initial temperature is 50-100 DEG C, maintaining for 1-5 min, then increasing the temperature to 200 DEG C-240 DEG C at a rate of 5-40 DEG C / min, maintaining for 1-10 min. The above detection method can quickly and accurately determine the twelve polyols and the banned substance diethylene glycol. The effective separation of the twelve polyols and the banned substance diethylene glycol is realized on the same spectrum, qualitative and quantitative analysis of various polyols can be carried out, and a simple and reliable analysis method is provided for quantitative monitoring of the polyols.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of pharmaceutical analysis and detection, in particular to a method for determining twelve polyols and a banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry. BACKGROUND

[0002] Polyols are alcohols containing two or more hydroxyl groups in the molecule. In cosmetic addition, polyols are generally used as solvents and mainly serve to moisturize and soothe the skin. Some alcohols have antibacterial effects. This makes polyols one of the important raw materials to replace traditional preservative systems. However, excessive use of polyols may cause irritation, skin allergy and other problems. Therefore, the addition amount of polyols should be controlled to ensure safety and control costs while playing the role of polyols.

[0003] Currently, there is no corresponding national standard for polyol methods. The detection method of polyol is mainly gas chromatography-mass spectrometry, but only 8 kinds of polyols are detected, and the types of polyols involved are limited. The detection method does not involve the banned substance diethylene glycol. Diethylene glycol may be brought into cosmetics as an impurity from other polyols.

[0004] Therefore, it is necessary to provide a method for simultaneously detecting the contents of twelve polyols and diethylene glycol to monitor the quality and safety of cosmetics. SUMMARY

[0005] Therefore, the technical problem to be solved by the present application is to provide a method for determining twelve polyols and a banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry. The method is stable and reliable, and has a low detection limit.

[0006] The present application provides a method for determining twelve polyols and a banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry, comprising:

[0007] A) dissolving the sample to be tested with a solvent to obtain a test solution;

[0008] Twelve polyols and diethylene glycol are dissolved with a solvent to obtain a reference solution;

[0009] B) determining the test solution and the reference solution by gas chromatography-mass spectrometry; the chromatographic column is a medium-polarity or weak-polarity chromatographic column;

[0010] Programmed temperature: initial temperature 50-100℃, maintained for 1-5min, then increased to 200℃-240℃ at a rate of 5-40℃ / min, maintained for 1-10min.

[0011] Preferably, the determination in step B) is specifically: determination by selected ion monitoring mode, qualitative determination by gas chromatography-mass spectrometry retention time and mass spectrometry characteristic ions, and calculation of the content of the polyhydric alcohol and diethylene glycol in the test sample according to the chromatographic peak area by external standard method.

[0012] Preferably, the solvent in step A) is ethanol.

[0013] Preferably, the chromatographic column in step B) is DB-624; the chromatographic column specifications are: 30 m x 0.320 mm x 1.8 μm.

[0014] Preferably, the programmed temperature in step B) is specifically: initial column temperature 80℃, holding for 2 min, increasing to 120℃ at a rate of 25℃ / min, holding for 2 min, then increasing to 140℃ at a rate of 5℃ / min, holding for 0 min, then increasing to 220℃ at a rate of 30℃ / min, holding for 4 min.

[0015] or

[0016] The programmed temperature is specifically: initial column temperature 80℃, holding for 2 min, increasing to 150℃ at a rate of 20℃ / min, holding for 3 min, then increasing to 220℃ at a rate of 30℃ / min, holding for 3 min.

[0017] Preferably, the detection conditions of the method are: detector: MS quadrupole mass spectrometer; ion mode: SIM, mass range 30-250.

[0018] Preferably, the mass spectrometry conditions in step B) are: injection port temperature 230℃; chromatography-mass spectrometry interface temperature: 250℃; ionization mode: EI; ion source: 230℃; quadrupole: 150℃; ionization energy: 70 eV.

[0019] Preferably, the carrier gas is helium; the carrier gas flow rate is 2 ml / min.

[0020] The injection mode is pulse split injection, split ratio 5:1, injection volume 1 μL-3 μL.

[0021] Preferably, the twelve polyhydric alcohols are 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol and ethylhexyl glycerin.

[0022] The 1,2-propanediol has a good linear relationship between the concentration 10 μg / mL-200 μg / mL and the peak area.

[0023] 2,3-Butanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0024] 1,3-Propanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0025] 1,2-Butanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0026] 1,3-Butanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0027] 1,2-Pentanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0028] 1,4-Butanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0029] Dipropylene glycol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0030] Glycerol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0031] 1,2-Hexanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0032] Octanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0033] Ethylhexylglycerin has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL ~ 200 μg / mL;

[0034] Diethylene glycol has a good linear relationship between the peak area and the concentration in the range of 1 μg / mL ~ 20 μg / mL.

[0035] Preferably, the sample to be tested is a cosmetic product;

[0036] The dosage form of the cosmetic product is water, cream, milk or mask.

[0037] Compared with the prior art, the present application provides a method for determining twelve polyols and the banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry, comprising: A) dissolving the sample to be tested with a solvent to obtain a test solution; dissolving twelve polyols and diethylene glycol with a solvent to obtain a control solution; B) determining the test solution and the control solution by gas chromatography-mass spectrometry; the chromatographic column is a medium-polarity or weak-polarity chromatographic column; the temperature program is: the initial temperature is 50-100 DEG C, maintained for 1-5 min, then the temperature is raised to 200 DEG C-240 DEG C at a rate of 5-40 DEG C / min, maintained for 1-10 min. The above detection method of the present application can quickly and accurately determine twelve polyols and the banned substance diethylene glycol. The effective separation of 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol, ethylhexyl glycerol and other polyols is realized on the same spectrum, and one or more than two polyols can be qualitatively and quantitatively analyzed, which provides a simple, rapid and reliable analysis method for the quantitative monitoring of polyols, and no toxic and harmful solvents such as methanol and acetonitrile are used. The method of the present application has high precision and accuracy, low detection limit and strong detection capacity, and is a high-efficiency, sensitive and accurate determination method. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is a blank solvent chromatogram;

[0039] Figure 2 is a chromatogram of thirteen mixed standard control samples;

[0040] Figure 3 is a chromatogram of a blank sample solution;

[0041] Figure 4 is a chromatogram of a test sample solution;

[0042] Figure 5 is a chromatogram of thirteen mixed standard control samples under the condition of Comparative Example 1;

[0043] Figure 5-1 is a chromatogram of 1,2-pentanediol control under the condition of Comparative Example 1;

[0044] Figure 5-2 is a chromatogram of 1,3-propanediol control under the condition of Comparative Example 1;

[0045] Figure 5-3 is a chromatogram of glycerol control under the condition of Comparative Example 1;

[0046] Figure 5-4 is a chromatogram of ethylhexyl glycerol control under the condition of Comparative Example 1;

[0047] Figure 5-5 is the chromatogram of the mixed standard control of 1,2-pentanediol, 1,3-propanediol, glycerol, ethylhexyl glycerin under the condition of Comparative Example 1;

[0048] Figure 6 is the chromatogram of the thirteen mixed standard controls under the condition of Comparative Example 2;

[0049] Figure 7 is the chromatogram of the thirteen mixed standard controls under the condition of Comparative Example 3;

[0050] Figure 8 is the chromatogram of the thirteen mixed standard controls under the condition of Comparative Example 4;

[0051] Figure 8-1 is the chromatogram of the glycerol control under the condition of Comparative Example 4;

[0052] Figure 8-2 is the chromatogram of the dipropylene glycol control under the condition of Comparative Example 4;

[0053] Figure 8-3 is the chromatogram of the mixed standard control of glycerol and dipropylene glycol under the condition of Comparative Example 4. DETAILED DESCRIPTION

[0054] The present application provides a method for determining twelve polyols and the banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry. Those skilled in the art can refer to the content herein and appropriately improve the process parameters to achieve. It is particularly important to note that all similar substitutions and changes are obvious to those skilled in the art, and they all belong to the scope of protection of the present application. The method and application of the present application have been described by the preferred embodiments, and the relevant personnel can obviously make changes or appropriate changes and combinations to the method and application herein without departing from the content, spirit and scope of the present application, to realize and apply the present application technology.

[0055] It should be noted that some terms are used in the specification and claims to refer to specific components. Those skilled in the art should understand that the same component can be referred to by different terms by the skilled person. The specification and claims do not distinguish components by the difference in terms, but by the difference in function. As mentioned throughout the specification and claims, "including" or "comprising" is an open term, which should be interpreted as "including but not limited to". The subsequent description in the specification is a preferred embodiment for implementing the present application, but the description is for the purpose of illustrating the general principles of the specification, and is not intended to limit the scope of the present application. The scope of protection of the present application is defined by the appended claims.

[0056] In the present application, the term ''and / or'', which describes the association relationship of the associated objects, indicates that there can be three kinds of relationships, for example, A and / or B can represent the following three cases: A exists alone, A and B exist simultaneously, and B exists alone.

[0057] In the present application, ''at least one'' means one or more, and ''a plurality of'' means two or more.

[0058] It should be understood that in various embodiments of the present application, the size of the sequence number of the above-mentioned processes does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of the processes should be determined according to their functions and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0059] Since polyols are generally added in cosmetics, the raw materials are not completely single components, but mixtures of isomers or mixtures of various alcohols, which show a group of peaks with similar chromatographic retention time on the chromatogram. The inventors use mass spectrometry to collect ion monitoring, adjust the parameters such as column temperature, carrier gas flow rate, split ratio, and select a suitable temperature program, so that the chromatographic retention time of the twelve polyols and diethylene glycol components is within 15 min, and the three peaks of dipropylene glycol are separated well between the main peak and the two secondary peaks. Due to the difference of raw materials, the two secondary peaks of dipropylene glycol in cosmetics are not prominent and can be ignored. According to the external standard method, the control peak area of dipropylene glycol can be calculated based on the main peak, or the total area of the three peaks can be calculated according to the actual test sample.

[0060] The detection method of the polyol described in the present application is determined by mass spectrometry in SIM mode, the chromatographic conditions are optimized, and the temperature programming method is selected, so that 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol, and ethylhexyl glycerol can be effectively separated on the same chromatogram. One or more polyols can be qualitatively and quantitatively analyzed, a simple, fast and reliable analysis method is provided for quantitative monitoring of polyols, and no toxic and harmful solvents such as methanol and acetonitrile are used.

[0061] The present application provides a method for determining twelve kinds of polyols and the banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry, comprising:

[0062] A) dissolving the sample to be tested with a solvent to obtain a test solution;

[0063] The twelve polyols and diethylene glycol are dissolved by a solvent to obtain a control solution;

[0064] B) The test solution and the control solution are determined by gas chromatography-mass spectrometry; the chromatographic column is a medium-polarity or weak-polarity chromatographic column;

[0065] Programmed temperature rising: the initial temperature is 50-100 DEG C, maintained for 1-5 min, then raised to 200-240 DEG C at a rate of 5-40 DEG C / min, maintained for 1-10 min.

[0066] The method for determining twelve polyols and the banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry provided by the application first dissolves the test sample by a solvent to obtain a test solution.

[0067] The test sample is cosmetics; the dosage form of the cosmetics is water, cream, milk or mask.

[0068] Specifically, the test sample can be commercially available cosmetics containing 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol, ethylhexyl glycerin or a mixture of raw materials thereof.

[0069] The extraction solution and the dilution solution dissolve 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol and ethylhexyl glycerin; in principle, any solvent that does not interfere with the detection of the test sample can be used, for example, one or a combination of methanol, acetonitrile, ethanol, dimethyl sulfoxide and the like, and the reagent grade thereof needs to reach HPLC grade or above. More preferably, the solvent is ethanol.

[0070] The mass g of the test sample and the volume mL of the solvent are in a mass ratio of 1g:25mL. The twelve polyols and diethylene glycol are dissolved by a solvent to obtain a control solution.

[0071] The twelve polyols are 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol and ethylhexyl glycerin.

[0072] The control product described in the application is a standard substance of 2,3-butanediol, CAS: 513-85-9, 1,2-propanediol, CAS: 57-55-6, 1,2-butanediol, CAS: 584-03-2, 1,3-butanediol, CAS: 107-88-0, 1,2-pentanediol, CAS: 543-92-0, 1,3-propanediol, CAS: 504-63-2, dipropylene glycol, CAS: 110-98-5, 1,2-hexanediol, CAS: 6920-22-5, 1,4-butanediol, CAS: 110-63-4, diethylene glycol, CAS: 111-46-6, octylene glycol, CAS: 1117-86-8, glycerol, CAS: 56-81-5, ethylhexyl glycerin, CAS: 70445-33-9, etc., all with a purity greater than 90% and with a standard certificate.

[0073] The test solution and the control solution are determined by gas chromatography-mass spectrometry.

[0074] The determination described in the application is specifically: the determination is carried out by selecting an ion monitoring mode, qualitative determination is carried out by gas chromatography-mass spectrometry retention time and mass spectrometry characteristic ions, and the content of polyols and diethylene glycol in the test product is calculated according to the chromatographic peak area by an external standard method.

[0075] More preferably, it is specifically:

[0076] The test solution and the control solution are sequentially injected to record the gas mass spectrum, the positions of the chromatograms of the control solution are attributed to the chromatographic peaks in the chromatogram of the test product, and the ion abundance ratios of the corresponding characteristic ions are compared, so as to determine whether the corresponding polyol is contained in the test product. For a substance containing multiple polyols, the mixed solution of the test product and the control product is detected, the obtained chromatogram is compared with the chromatogram of the test product, and the ion abundance ratios of the corresponding characteristic ions are compared, so as to determine the characteristic ion chromatographic peak and the ion abundance ratio consistent with the control product in the test product solution.

[0077] The above quantitative detection method can be used to calculate the content of various polyols and diethylene glycol in the test product according to the chromatographic peak area by an external standard method.

[0078] The chromatographic column is a medium-polarity or weak-polarity chromatographic column; the chromatographic column is DB-624; the chromatographic column specification is: 30m x 0.320mm x 1.8μm.

[0079] The application preferably uses the above chromatographic column, which can well separate the components of the sample, and the chromatographic peak separation degree is good.

[0080] The temperature programming of the present application is as follows: the initial temperature is 50-100 DEG C, maintaining for 1-5 min, then increasing the temperature to 200-240 DEG C at a rate of 5-40 DEG C / min, maintaining for 1-10 min.

[0081] In one of the preferred embodiments of the present application, the temperature programming is as follows: the initial column temperature is 80 DEG C, maintaining for 2 min, increasing the temperature to 120 DEG C at a rate of 25 DEG C / min, maintaining for 2 min, increasing the temperature to 140 DEG C at a rate of 5 DEG C / min, maintaining for 0 min, increasing the temperature to 220 DEG C at a rate of 30 DEG C / min, maintaining for 4 min.

[0082] In one of the preferred embodiments of the present application, the temperature programming is as follows: the initial column temperature is 80 DEG C, maintaining for 2 min, increasing the temperature to 120 DEG C at a rate of 25 DEG C / min, maintaining for 2 min, increasing the temperature to 140 DEG C at a rate of 5 DEG C / min, maintaining for 0 min, increasing the temperature to 220 DEG C at a rate of 30 DEG C / min, maintaining for 4 min.

[0083] The present application has high resolution and low detection limit by controlling the temperature programming.

[0084] The detection conditions of the method of the present application are as follows: detector: MS four-stage rod mass spectrometer; ion mode: SIM, mass range: 30-250.

[0085] The mass spectrometry conditions are as follows: injection port temperature: 230 DEG C; chromatography-mass spectrometry interface temperature: 250 DEG C; ionization mode: EI; ion source: 230 DEG C; four-stage rod: 150 DEG C; ionization energy: 70 eV.

[0086] The carrier gas of the present application is helium, and the purity is greater than or equal to 99.999%, and the flow rate of the carrier gas is 2 ml / min.

[0087] The injection mode of the present application is pulse split injection, the split ratio is 5:1, and the injection amount is 1-3 muL.

[0088] According to the present application, the 1,2-propanediol has good linear relationship with the peak area in the concentration range of 10-200 mu g / mL.

[0089] 2,3-Butanediol has good linear relationship with the peak area in the concentration range of 10-200 mu g / mL.

[0090] 1,3-Propanediol has good linear relationship with the peak area in the concentration range of 10-200 mu g / mL.

[0091] 1,2-Butanediol has good linear relationship with the peak area in the concentration range of 10-200 mu g / mL.

[0092] 1,3-Butanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0093] 1,2-Pentanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0094] 1,4-Butanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0095] Dipropylene glycol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0096] Glycerol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0097] 1,2-Hexanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0098] Octanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0099] Ethylhexyl glycerin has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL-200 μg / mL;

[0100] Diethylene glycol has a good linear relationship between the peak area and the concentration in the range of 1 μg / mL-20 μg / mL.

[0101] The method of the application has a large linear range and good linear results.

[0102] The instrument detection limit of 2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, dipropylene glycol, 1,2-hexanediol, octanediol and ethylhexyl glycerin in the application is 1.6 μg / mL, the instrument quantitative limit is 4.8 μg / mL, the method detection limit is 40 mg / kg, and the method quantitative limit is 120 mg / kg.

[0103] The instrument detection limit of glycerol in the application is 0.6 μg / mL, the instrument quantitative limit is 1.8 μg / mL, the method detection limit is 15 mg / kg, and the method quantitative limit is 45 mg / kg.

[0104] The instrument detection limit of diethylene glycol in the application is 0.2 μg / mL, the instrument quantitative limit is 0.6 μg / mL, the method detection limit is 5 mg / kg, and the method quantitative limit is 15 mg / kg.

[0105] The detection limit and the quantitative limit of the method are low, the twelve polyols and the banned substance diethylene glycol with low content can be detected, and the product quality is improved.

[0106] The application provides a method for determining twelve polyols and a banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry, comprising the following steps: A) dissolving a sample to be detected by using a solvent to obtain a sample solution to be detected; dissolving the twelve polyols and the banned substance diethylene glycol by using a solvent to obtain a control solution; B) determining the sample solution to be detected and the control solution by using a gas chromatography-mass spectrometry method; the chromatographic column is a medium-polarity or weak-polarity chromatographic column; the temperature program is as follows: the initial temperature is 50-100 DEG C, the temperature is maintained for 1-5 min, then the temperature is raised to 200-240 DEG C at a rate of 5-40 DEG C / min, and the temperature is maintained for 1-10 min. The above-mentioned determination method can quickly and accurately determine the twelve polyols and the banned substance diethylene glycol. The effective separation of the polyols such as 1,2-propylene glycol, 2,3-butylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,4-butylene glycol, diethylene glycol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol and ethylhexyl glycerin is realized on the same spectrum, the qualitative and quantitative analysis of one or more than two polyols can be carried out, a simple, quick and reliable analysis method is provided for the quantitative monitoring of the polyols, and no toxic and harmful solvents such as methanol and acetonitrile are used. The method has high precision, high accuracy and low detection limit, and has strong detection capacity, and is a high-efficiency, sensitive and accurate determination method.

[0107] The application provides a method for determining the content of twelve polyols and diethylene glycol in cosmetics, which has the advantages of simple operation, short analysis time, low detection limit, strong anti-interference ability and the use of ethanol as the extraction solvent, and no toxic and harmful solvents such as methanol and acetonitrile are used.

[0108] In order to further illustrate the application, the method for determining twelve polyols and a banned substance diethylene glycol in cosmetics by gas chromatography-mass spectrometry provided by the application is described in detail in combination with the following examples.

[0109] Unless otherwise indicated, all temperatures described in the examples below are in degrees Celsius. The gas chromatograph used is an Agilent 7890A, and the electronic balance used is an XPE204 or an ML204. Unless otherwise specified in the examples, the techniques or conditions are carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. The reagents are purchased from Aldrich, Arco, Alfa, MERK, Scharlau, Aldrich, Xilong Scientific, etc.

[0110] Example 1 (detection limit and quantitative limit)

[0111] The specific preparation methods of the solutions are as follows:

[0112] Blank solution and diluent, extractant (ethanol)

[0113] 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol, ethylhexyl glycerol control solution: accurately weigh the corresponding polyol control product, accurately weigh, and dilute with a blank solution to prepare a solution containing 10-200 mg / L per 1 mL.

[0114] Diethylene glycol control solution: accurately weigh the corresponding diethylene glycol control product, accurately weigh, and dilute with a blank solution to prepare a solution containing 1-20 mg / L per 1 mL.

[0115] Test sample solution: accurately weigh the test sample, accurately weigh, and dilute with a blank solution, shake well, and record as the test sample solution.

[0116] The control external standard method is a conventional method in the art, and the steps are: respectively prepare blank solution (i.e. diluent, extractant), control solution, test sample solution, sequentially sample and record gas chromatogram, according to the quantitative ion peak area of each control solution, calculate the content of various polyols and diethylene glycol in the test sample according to the external standard method formula. For substances containing multiple polyols or diethylene glycol, the mixture solution of the test sample and the control sample can be detected, the obtained chromatogram is compared with the test sample chromatogram, and the ion abundance ratio of the corresponding characteristic ions is compared to determine the characteristic ion chromatographic peak area consistent with the control sample in the test sample solution.

[0117] The present application is verified by a systematic methodology, and the method is exclusive and reliable, and meets the detection requirements.

[0118] Table 1: Retention time, quantitative and qualitative selection ion, and resolution result table of polyols

[0119]

[0120]

[0121] The detection method of the contents of twelve polyols and diethylene glycol in cosmetics is as follows:

[0122] Use 8890 gas chromatograph, detector is 5977B four-stage rod mass spectrometer detector, and the instrument conditions are as follows:

[0123] Chromatographic column: DB-624 (30 m x 320 μm (inner diameter) x 1.8 μm (film thickness));

[0124] Temperature program: initial column temperature 80 °C, hold for 2 min, ramp to 150 °C at 20 °C / min, hold for 3 min, ramp to 220 °C at 30 °C / min, hold for 3 min.

[0125] Injection port temperature: 230 °C; injection mode: pulse split, split ratio 5:1, injection volume: 1 μL;

[0126] Carrier gas: helium, purity > 99.999 %, flow rate: 2.0 mL / min;

[0127] Chromatograph-mass spectrometer interface temperature: 250 °C; ionization mode: EI; ion source: 230 °C; quadrupole: 150 °C;

[0128] Ionization energy: 70 eV; acquisition mode: selected ion monitoring (SIM), mass range: 30-250.

[0129] Solution preparation:

[0130] The detection limit and the quantification limit of the polyols and diethylene glycol were determined as shown in Table 2 by adding the lowest acceptable concentration of the sample to the blank sample, testing independently for not less than 10 times (n > 10), calculating the relative deviation (s) of the results, taking 3 times the relative deviation as the detection limit, and taking 10 times the relative deviation as the quantification limit.

[0131] Table 2 Detection limit and quantification limit of the polyols

[0132]

[0133]

[0134] Example 2 (linearity test)

[0135] The detection method was the same as in Example 1.

[0136] Solution preparation:

[0137] Accurately weigh 0.2 g (accurate to 0.0001 g) of each polyol and diethylene glycol standard substance into a 10 mL volumetric flask, and prepare a standard stock solution with a concentration of 20 mg / mL using a blank solution; pipette 0.5 mL (0.05 mL for diethylene glycol) of each single standard stock solution into a 10 mL volumetric flask, and prepare a mixed standard stock intermediate solution with a concentration of 1 mg / mL (0.1 mg / mL for diethylene glycol) using a blank solution; accurately measure 0.1 mL, 0.2 mL, 0.5 mL, 1 mL, and 2 mL, respectively, into 10 mL volumetric flasks, and dilute to the calibration mark with a blank solution, shake well, and prepare the mixed standard stock intermediate solution into 10, 20, 50, 100, and 200 mg / L (1, 2, 5, 10, and 20 mg / L for diethylene glycol) standard series solutions, respectively, as linear solutions No. 2-6. Accurately pipette 1 μL of each linear solution No. 1-6 into a gas chromatograph for determination, repeat the determination 3 times (C = 3), and perform linear regression equation with the concentration (x) and peak area (y) to obtain the regression equation (N = 6); the results are shown in Table 3.

[0138] Table 3 Determination results of polyol standard curve (N = 6, C = 3)

[0139]

[0140]

[0141]

[0142]

[0143] As shown in Table 3, the curves of the twelve polyols and diethylene glycol are stable, and 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol, and ethylhexyl glycerol have good linear relationships in the concentration range of 10-200 μg / mL, and diethylene glycol has a good linear relationship in the concentration range of 1-20 μg / mL.

[0144] Example 3 (precision)

[0145] The detection method is the same as in Example 1.

[0146] The linear No. 2 solution under the linear test in Example 2 was precisely measured, and the quantitative ion peak area was recorded for 6 times in succession, and the RSD of the quantitative ion peak area of the polyol and diethylene glycol was calculated. The RSD of the quantitative ion peak area of 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol, and ethylhexyl glycerol was 1.72%, 1.59%, 1.65%, 1.31%, 1.67%, 2.26%, 2.25%, 5.45%, 4.15%, 4.33%, 2.77%, 4.88%, and 8.53% respectively, all less than 10.0%, and the detection method has good precision.

[0147] Example 4 (recovery rate test)

[0148] The detection method is the same as Example 1.

[0149] Solution configuration:

[0150] The blank matrix sample is a sample of different matrixes with 0 content of 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol, and ethylhexyl glycerol.

[0151] Control stock solution 1: 0.2 g (accurate to 0.0001 g) of each polyol and diethylene glycol standard substance was accurately weighed and placed in a 10 mL volumetric flask, and a standard control stock solution with a concentration of 20 mg / mL was prepared with a blank solution.

[0152] Control stock solution 2: 0.5 mL (0.05 mL of diethylene glycol) of each single standard control stock solution 1 was taken and placed in a 10 mL volumetric flask, and a mixed standard control stock solution with a concentration of 1 mg / mL (0.1 mg / mL of diethylene glycol) was prepared with a blank solution.

[0153] Control solution: the mixed standard stock intermediate solution with a concentration of 1 mg / mL (0.1 mg / mL of diethylene glycol) was prepared with a blank solution according to Example 2; 0.05 mL, 0.1 mL, 0.2 mL, 0.5 mL, 1 mL, and 2 mL were accurately measured and placed in a 10 mL volumetric flask, and the mixed standard stock intermediate solution was diluted to the mark with a blank solution, shaken well, and the mixed standard stock intermediate solution was prepared into 5, 10, 20, 50, 100, and 200 mg / L (0.5, 1, 2, 5, 10, and 20 mg / L of diethylene glycol) standard series solutions.

[0154] Spiked test sample solution: The blank matrix sample was precisely weighed, placed in a 25 mL colorimetric tube, and 0.25 mL, 0.50 mL, and 1.25 mL of the control stock solution 2 were precisely added, respectively, and each was prepared in triplicate. The blank solution was diluted to the calibration mark, shaken, ultrasonically extracted for 20 min, centrifuged if necessary, filtered through a 0.45 μm filter membrane, and the filtrate was obtained. The results were as follows: (1) polyol mix 12 was 250 mg / kg, and diethylene glycol was 25 mg / kg; (2) polyol mix 12 was 500 mg / kg, and diethylene glycol was 50 mg / kg; (3) polyol mix 12 was 1250 mg / kg, and diethylene glycol was 125 mg / kg. The spiked test sample solution was prepared.

[0155] Operation: The blank solution, the control solution, and each spiked test sample solution were determined, respectively, and the recovery rate was calculated by the external standard method. The results were as shown in Table 4.

[0156] Table 4: Recovery results of polyols added to each matrix

[0157]

[0158]

[0159]

[0160] According to the above results, the recovery rates of polyols and diethylene glycol in the three matrices were in the range of 80%-115%, and the RSDs were in the range of 0.34%-5.1%. The detection method of the present application has high accuracy.

[0161] Example 5 (sample repeatability test)

[0162] The detection method was the same as that in Example 1.

[0163] Solution preparation:

[0164] Control solution: The mixed standard intermediate stock solution was prepared by diluting the blank solution to a concentration of 1 mg / mL (diethylene glycol 0.1 mg / mL) according to Example 2; 0.05 mL, 0.1 mL, 0.2 mL, 0.5 mL, 1 mL, and 2 mL were precisely measured and placed in 10 mL volumetric flasks, respectively, and diluted to the calibration mark with the blank solution, shaken, and the mixed standard intermediate stock solution was prepared into 5, 10, 20, 50, 100, and 200 mg / L (diethylene glycol 0.5, 1, 2, 5, 10, and 20 mg / L) standard series solutions, respectively.

[0165] The sample was a common cosmetic product containing the target to be detected on the market;

[0166] Test sample solution: The sample was precisely weighed, placed in a 25 mL colorimetric tube, diluted with a blank solution to the calibration mark, shaken, ultrasonically extracted for 20 min, centrifuged if necessary, filtered through a 0.45 μm filter membrane, and obtained.

[0167] Operation: Six test bottle solutions were prepared from the same test sample, and the blank solution, the control solution and the test sample solution were respectively determined, and the content was calculated according to the external standard method. The results are shown in Table 5.

[0168] Table 5: Reproducibility of polyols in various matrices

[0169]

[0170]

[0171] According to the above results, the RSD of the content of polyols in several matrix samples is 0.41%-5.64%, and the reproducibility of the detection method of the present application is good.

[0172] When the method validation is completed, a single standard or corresponding mixed control solution can also be prepared when detecting the sample, and the content of each compound is detected according to the external standard method.

[0173] In summary, the detection method of polyols and diethylene glycol described in the present application is simple to operate, which can more accurately determine the content of polyols, and at the same time can detect the banned substance diethylene glycol introduced by polyol raw materials, the analysis time is short, and ethanol is used as a solvent, without using toxic and harmful reagents such as methanol and acetonitrile.

[0174] Comparative Example 1

[0175] The detection method and conditions disclosed in the patent application CN104345096A "A rapid detection method of polyols in cosmetics" were used to determine the concentration of the control (mixed control) of 100 mg / L, and the detection results are shown in Figure 5 .

[0176] From Figure 5 It can be seen that twelve polyols and diethylene glycol, a total of thirteen target substances, are separated into eleven target peaks under this condition; there are individual target substances that are overlapped or cannot be determined. By comparing the determination of individual target substance controls under the same conditions, it is known that the retention time of 1-2-pentanediol is 14.183 min, as Figure 5-1 , the retention time of 1-3-propanediol is 14.209 min, as Figure 5-2 , and Figure 5 There is only one target peak at 14.186 min in the corresponding time period; therefore, 1-2-pentanediol and 1-3-propanediol are overlapped. As Figure 5-3 It is known that the retention time of glycerol is 19.429 min, asFigure 5-4 Ethylhexylglycerin retention time is 19.448 min, Figure 5 There is only one target peak at 19.448 min in the corresponding time period; therefore, glycerin and ethylhexylglycerin overlap. Further determination of 1-2-pentanediol, 1-3-propanediol, glycerin, and ethylhexylglycerin mixed control under the same conditions as Figure 5-5 Only two target peaks of 14.178 min and 19.429 min are obtained; thus, it is proved that 1-2-pentanediol and 1-3-propanediol cannot be completely separated under the method conditions, and glycerin and ethylhexylglycerin cannot be completely separated, and it is concluded that this method is not suitable for the detection of twelve polyols and diethylene glycol.

[0177] Comparative Example 2

[0178] Using the detection method and conditions disclosed in the patent application CN114062572A "A detection method for polyols and applications", the determination of the control concentration (mixed control) is 100 mg / L, and the detection results are as shown in Figure 6 .

[0179] From Figure 6 It can be seen that the thirteen target objects of twelve polyols and diethylene glycol are separated into thirteen target peaks under this condition; by determining the individual target control under the same conditions and comparing the chromatograms, it is found that the target peaks of 1,2-pentanediol (6.982 min) and 1,3-propanediol (7.026 min) cannot be completely separated, and it is concluded that this method is not suitable for the detection of twelve polyols and diethylene glycol.

[0180] Comparative Example 3

[0181] Using the detection method and conditions disclosed in the literature "Determination of polyol moisturizers in cosmetics by gas chromatography" published in Chemical Industry on June 2010 by Ba Zhijuan et al., the determination of the control concentration (mixed control) is 100 mg / L, and the detection results are as shown in Figure 7 .

[0182] From Figure 7 It can be seen that the thirteen target objects of twelve polyols and diethylene glycol are separated into ten target peaks under this condition, and there are individual target overlaps or undetectable conditions. By determining the individual target control under the same conditions and comparing the chromatograms, it is found that octylglycerin, ethylhexylglycerin, and glycerin cannot be detected, and as Figure 7 1,2-pentanediol (19.115 min) and 1,3-propanediol (19.197 min) cannot be completely separated, and it is concluded that this method is not suitable for the detection of twelve polyols and diethylene glycol.

[0183] Comparative Example 4

[0184] Using the detection methods and conditions disclosed in Tang Yuping's 2020.2 publication, "Simultaneous Determination of Eight Polyols in Cosmetics by Gas Chromatography," a reference standard concentration (mixed control) of 100 mg / L was determined. The detection results are as follows: Figure 8 As shown.

[0185] Depend on Figure 8 It can be seen that under these conditions, a total of twelve target compounds, including twelve polyols and diethylene glycol, yielded twelve target peaks, with some compounds overlapping or being undetectable. By comparing the spectra of individual target compounds under the same conditions, it was found that the target peaks of 1,3-propanediol (10.258 min) and 1,2-butanediol (10.306 min) could not be completely separated. Figure 8-1 Glycerol retention time (14.027 min), such as Figure 8-2 The retention time of dipropylene glycol was 13.988 min, while Figure 8 There was only one target peak at 13.988 min in the corresponding time period; further testing was conducted under the same conditions on a mixed reference standard of glycerol and dipropylene glycol. Figure 8-3 A target peak was obtained at 14.026 min; this proves that glycerol and dipropylene glycol cannot be completely separated under the conditions of this method, and that this method is not suitable for the detection of twelve polyols and diethylene glycol.

[0186] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for determining twelve polyols and a banned substance diethylene glycol in a cosmetic by gas chromatography-mass spectrometry, comprising: A) dissolving a sample to be tested with a solvent to obtain a test solution; dissolving twelve polyols and diethylene glycol with a solvent to obtain a reference solution; B) determining the test solution and the reference solution by gas chromatography-mass spectrometry; the determination is specifically: determining by selected ion monitoring mode, qualitatively determining by gas chromatography-mass spectrometry retention time and mass spectrometry characteristic ions, and calculating the content of polyols and diethylene glycol in the test sample according to the chromatographic peak area by external standard method; the chromatographic column is DB-624; the chromatographic column specification is: 30 m x 0.320 mm x 1.8 μm; the programmed temperature rising is: the initial temperature is 50-100 ℃, maintaining for 1-5 min, then rising to 200-240 ℃ at a rate of 5-40 ℃ / min, maintaining for 1-10 min; the mass spectrometry conditions are: the inlet temperature is 230 ℃; the chromatography-mass spectrometry interface temperature is 250 ℃; the ionization mode is EI; the ion source is 230 ℃; the quadrupole rod is 150 ℃; the ionization energy is 70 eV; the detector is MS quadrupole mass spectrometry; the ion mode is SIM, and the mass range is 30-250; the twelve polyols are 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-butanediol, dipropylene glycol, glycerol, 1,2-hexanediol, octylene glycol and ethylhexyl glycerin.

2. The method of claim 1, wherein, the solvent in step A) is ethanol.

3. The method of claim 1, wherein, the programmed temperature rising in step B) is specifically: the initial column temperature is 80 ℃, maintaining for 2 min, rising to 120 ℃ at a rate of 25 ℃ / min, maintaining for 2 min, then rising to 140 ℃ at a rate of 5 ℃ / min, maintaining for 0 min, then rising to 220 ℃ at a rate of 30 ℃ / min, maintaining for 4 min; or the programmed temperature rising is specifically: the initial column temperature is 80 ℃, maintaining for 2 min, rising to 150 ℃ at a rate of 20 ℃ / min, maintaining for 3 min, then rising to 220 ℃ at a rate of 30 ℃ / min, maintaining for 3 min.

4. The method of claim 1, wherein, the carrier gas is helium; the carrier gas flow rate is 2 ml / min; the injection mode is pulse split injection, the split ratio is 5:1, and the injection amount is 1-3 μL.

5. The method of claim 1, wherein, the 1,2-propanediol has a good linear relationship between the peak area and the concentration in the range of 10-200 μg / mL; the 2,3-butanediol has a good linear relationship between the peak area and the concentration in the range of 10-200 μg / mL; the 1,3-propanediol has a good linear relationship between the peak area and the concentration in the range of 10-200 μg / mL; the 1,2-butanediol has a good linear relationship between the peak area and the concentration in the range of 10-200 μg / mL; the 1,3-butanediol has a good linear relationship between the peak area and the concentration in the range of 10-200 μg / mL; the 1,2-pentanediol has a good linear relationship between the peak area and the concentration in the range of 10-200 μg / mL; 1,4-butanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL~200 μg / mL; Dipropylene glycol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL~200 μg / mL; Glycerol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL~200 μg / mL; 1,2-hexanediol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL~200 μg / mL; Octyl glycol has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL~200 μg / mL; Ethylhexyl glycerin has a good linear relationship between the peak area and the concentration in the range of 10 μg / mL~200 μg / mL; Diethylene glycol has a good linear relationship between the peak area and the concentration in the range of 1 μg / mL~20 μg / mL.

6. The method of claim 1, wherein, The dosage form of the cosmetic is water, cream, milk or mask.

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