Method for rapidly identifying organic fluorides in oral care product and raw materials thereof

Abstract

According to the method for rapidly identifying the organic fluoride in the oral care product and the raw materials of the oral care product, the raw materials referred to by the scheme are raw materials of organic fluorine sources, such as an oxilafluorine raw material, and the method can be used for rapidly identifying the organic fluoride in the oral care product through pretreatment of an object to be detected and setting of liquid chromatography-tandem mass spectrometry conditions. Rapid qualitative and quantitative detection of organic fluorides such as 3-pyridine methanol hydrogen fluoride containing hydrofluoride and in a non-salt form, bis (hydroxyethyl) amino propyl hydroxyethyl hexadecylamine, bis (hydroxyethyl) amino propyl hydroxyethyl oleylamine, bis (hydroxyethyl) amino propyl hydroxyethyl octadecylamine, hexadecylamine, diclafon and octadecylamine is realized; the content of the organic fluoride ions can be indirectly obtained, and the blank of organic fluoride detection in the field of oral care products is filled.

Description

Technical Field

[0001] The invention relates to the field of chemical detection, and in particular to a method for quickly identifying organic fluorides in oral care products and raw materials thereof. Background Art

[0002] Dental caries, gingivitis, pulpitis, etc. are common oral health problems worldwide, affecting people's daily life and physical health to varying degrees. It is well known that fluoride has an anti-caries effect, can promote the remineralization of tooth hard tissues and inhibit demineralization. Over the years, the use of fluoride in different forms and different application scenarios has reduced the prevalence of tooth hard tissue loss caused by dental caries. Fluoride plays an important role in preventing dental caries, strengthening teeth, and inhibiting bacteria and sterilization when added to toothpaste.

[0003] With the development of the industry, the fluorides added to fluoride toothpaste on the market are no longer limited to inorganic fluorides such as sodium fluoride, sodium monofluorophosphate, and stannous fluoride. Organic fluorides represented by Olaflur and dectaflur have been allowed to be added to oral care products such as toothpaste and mouthwash, with the maximum allowed addition amount being 0.15% (calculated as fluoride).

[0004] Unlike inorganic fluorides that are randomly distributed in the oral cavity, organic fluoride compounds have better anti-caries effects due to their better stability and durability, as well as weak acidity after dissolution. Currently, the anti-caries toothpastes on the market have added organic fluorides such as olaflu and dexaflut at different concentrations for children of different age groups. However, there are few research reports on the detection methods of organic fluorides such as 3-pyridinemethanol hydrogen fluoride, dexaflut, and cetylamine hydrofluoride in oral care products. Most detection methods still use ion chromatography, fluorine electrode method, etc. to determine fluoride ions, and this method of detecting fluoride ions cannot distinguish whether its source is organic fluoride or inorganic fluoride. This situation brings many problems: on the one hand, it is difficult for quality inspection departments to accurately evaluate the actual content and efficacy of organic fluorine in oral care products, which affects product quality control and R&D optimization; on the other hand, it leads to the irregular addition of organic fluorine in some oral care products on the market, which is difficult to detect, thus causing damage to consumers. Summary of the invention

[0005] The purpose of the present invention is to provide a method for quickly identifying organic fluorides in oral care products and their raw materials, which can identify organic fluorides with different carbon chain lengths and different saturations and their fluoride ion contents, and has the advantages of being simple, rapid, efficient and quantitatively accurate.

[0006] To achieve the above objectives, the present technical solution provides a method for quickly identifying organic fluorides in oral care products and their raw materials, comprising the following steps: Get the object to be tested; The object to be tested is ultrasonically dissolved with water to obtain a first solution, and the first solution is pre-treated twice to obtain a solution to be tested, wherein when the object to be tested is an oral care product raw material, mouthwash and spray, the first solution is diluted with water and methanol step by step to obtain a solution to be tested; when the object to be tested is a toothpaste-type oral care product, the first solution is diluted with water to obtain an analysis solution, and a solid phase extraction column is activated with methanol and water in sequence, and the analysis solution is purified through the column to obtain a purified solution, which is rinsed with purified water and then eluted with methanol to collect the solution to be tested; The solution to be tested is detected by liquid chromatography-tandem mass spectrometry in MRM mode to obtain a chromatogram, wherein the chromatographic column of the liquid chromatography is an Athena C4 or C8 analytical column, wherein when the Athena C4 analytical column is used, the mobile phase A is methanol, and the mobile phase B is 0.1% formic acid water, and when the C8 analytical column is used, the mobile phase A is methanol, and the mobile phase B is a 5-10Mmol / L ammonium acetate solution containing 0.1% formic acid, and the elution method is gradient elution; The quantitative or qualitative analysis of organic fluoride can be performed by qualitative and quantitative ion pairs.

[0007] It should be noted that, whether the analyte is an oral care product raw material, a mouthwash and spray, or a toothpaste-type oral care product, the concentration of the test solution needs to be controlled within the linear range of the target compound. The analyte to which this scheme is applicable is any one or a combination of the seven organic fluorides of 3-pyridinemethanol hydrogen fluoride, bishydroxyethylaminopropylhydroxyethylhexadecylamine, bishydroxyethylaminopropylhydroxyethyloleylamine, bishydroxyethylaminopropylhydroxyethyloctadecylamine, hexadecylamine, diketafur and octadecylamine.

[0008] It should be noted that the raw materials for oral care products referred to in this scheme are raw materials of organic fluorine sources, such as olafluor raw materials, etc.

[0009] Regarding the analyte of this scheme, the pyridine ring structure of 3-pyridinemethanol hydrofluoride gives it certain antibacterial properties, which can help inhibit the growth of harmful bacteria in the mouth and reduce problems such as bad breath and tooth decay caused by bacterial growth. At the same time, the released fluoride ions can react with minerals on the surface of teeth to enhance the acid resistance of tooth enamel and prevent tooth decay; bishydroxyethylaminopropylhydroxyethylhexadecylamine, bishydroxyethylaminopropylhydroxyethyloleylamine and bishydroxyethylaminopropylhydroxyethyloctadecylamine are all olaflurane non-salt structures and their analogs; hexadecylamine as an effective Organic fluoride can slowly release fluoride ions in the oral environment to react with hydroxyapatite in teeth to form fluoroapatite that is less soluble in acid, thereby enhancing the tooth's resistance to acid erosion and effectively preventing tooth decay; diketafur can not only provide fluoride ions to prevent tooth decay, but also form a protective film on the tooth surface due to its long-chain unsaturated structure, preventing acidic substances and bacteria in the oral cavity from contacting the teeth, reducing the risk of tooth decay; the fluoride ions released by the hydrofluoric acid salts of hexadecylamine and octadecylamine can enhance the tooth's resistance to tooth decay and maintain oral health. Therefore, these seven organic fluorides may all be added to oral care products and their organic fluoride source raw materials, and this scheme can use liquid chromatography-tandem mass spectrometry to detect these organic fluoride sources.

[0010] In some embodiments, the mass spectrometry conditions for liquid chromatography-tandem mass spectrometry detection of the test solution are: ion source ESI+, ion source voltage 5500, curtain gas 35 psi, ion source temperature 500°C, spray gas GS1 50 psi, auxiliary heating gas GS2 50 psi.

[0011] The mass spectrometry parameters of the organic fluoride in this scheme are shown in Table 1 below: Table 1 Mass spectrometry parameters of organic fluorides .

[0012] About the pre-processing of the object to be tested in this scheme: When the test object is oral care product raw materials, mouthwash and spray, the first solution is diluted stepwise with water and methanol to obtain the test solution, wherein the first solution is diluted with water to no more than 10 ppm and with methanol to 1-500 ppb.

[0013] When the object to be tested is a toothpaste-type oral care product, it is dissolved in water to obtain an analysis solution, 1-3 ml of the analysis solution is taken for column purification, and the HLB solid phase extraction column is activated and purified with methanol and water 1-3 times the volume of the analysis sample solution in sequence, rinsed with purified water 1-3 times the volume of the analysis sample solution, eluted and collected with 1-5 times the volume of methanol, and the test solution was obtained after constant volume with methanol.

[0014] Regarding the liquid chromatography conditions of this scheme: The chromatographic column of the liquid chromatography conditions of this scheme uses Athena C4 or C8, with a specification size of 2.1×100 mm, 5µm; the flow rate is set to 0.3~0.5 ml / min, the column temperature is 35℃, and the elution conditions of the gradient elution are: 0~0.5 min methanol 80%; 0.5~4 min, methanol 80%~95%; 4.1~5.5 min, methanol 80%.

[0015] When it is necessary to qualitatively identify organic fluorides, take 7 kinds of organic fluoride standards and dissolve them in methanol solution to obtain an organic fluorine source standard solution. Take the organic fluorine source standard solution for detection under the same liquid chromatography and mass spectrometry conditions. The retention time of the chromatogram of the test solution and the retention time of the chromatogram of the organic fluorine source standard solution, and the abundance ratio of the characteristic ions to the characteristic ions in the organic fluorine source standard solution of the corresponding concentration are used for qualitative identification. If the relative deviation of the retention time is not greater than 5%, and the abundance of the characteristic ions in the test solution and the characteristic ion abundance of the organic fluorine source standard solution are within the allowable deviation, it is considered that the corresponding organic fluoride is identified, wherein the relative abundance is consistent with the relative abundance of the organic fluorine source standard solution, and the relative abundance deviation does not exceed the provisions of Table 2: Table 2 Permissible deviation of relative ion abundance for qualitative confirmation (in percentage)

[0016] When quantitative detection of 7 kinds of organic fluorides is required, 7 kinds of organic fluoride standards are taken and dissolved in methanol to obtain standard working solutions of different concentrations. The standard working solutions are respectively detected under the same chromatographic and mass spectrometric conditions, and a standard substance concentration-response intensity external standard method curve is drawn based on the detection results, wherein the standard substance concentration-response intensity external standard method curve records the relationship between the concentration of organic fluorides and the response intensity, and the corresponding organic fluoride content is obtained based on the standard substance concentration-response intensity external standard method curve according to the response intensity of the solution to be tested in the liquid chromatograph.

[0017] Specifically, a series of standard solutions of organic fluorine sources are injected in sequence from low to high concentrations (not less than 5 concentration points), and an external standard method curve of standard substance concentration-response intensity is drawn according to the standard substance concentration-response intensity. When the content of organic fluoride in the test solution exceeds the linear range, the test solution is further diluted and then sampled and analyzed to ensure that its concentration is within the range of the calibration curve.

[0018] In some embodiments, the concentration of the standard working solution of the organic fluorine source is 1-500 µg / L.

[0019] In addition, the content of organic fluoride in the solution to be tested (based on the structure without hydrofluoride) is calculated according to the following formula: ; Where X i : Content of organic fluoride, mg / g; C i is the measured concentration of organic fluoride, μg / L; F is the dilution factor; v is the final fixed volume, mL; m is the sample mass of the object to be measured, g.

[0020] Compared with the prior art, this technical solution has the following characteristics and beneficial effects: This scheme uses liquid chromatography-tandem mass spectrometry detection combined with targeted pretreatment of the test objects to perform qualitative analysis on seven organic fluorides in oral care products and their raw materials, including 3-pyridinemethanol hydrogen fluoride, bis(hydroxyethylaminopropylhydroxyethylhexadecylamine, bis(hydroxyethylaminopropylhydroxyethyloleylamine, bis(hydroxyethylaminopropylhydroxyethyloctadecylamine), diketafiorate, hexadecylamine and octadecylamine, and accurately identify the source of organic fluorine. This solves the problem that it is difficult for quality inspection departments to accurately evaluate the actual content of organic fluorine in oral care products, which is beneficial to product quality control and R&D optimization. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the total ion spectrum obtained using a pentafluorophenyl column with methanol and 0.1% formic acid water as the mobile phase.

[0022] Figure 2 This is the ion spectrum of some organic fluorides obtained using a pentafluorophenyl column, methanol and 0.1% ammonium formic acid acetate solution as the mobile phase.

[0023] Figure 3 This is the total ion spectrum obtained using a C4 column with methanol and 0.1% ammonium formate acetate as the mobile phase.

[0024] Figure 4 The ion spectra of various organic fluorides were obtained using a C4 column with methanol and 0.1% ammonium formate acetate as the mobile phase.

[0025] Figure 5 This is the total ion spectrum of organic fluorides using a C4 column with methanol and 0.1% formic acid water as the mobile phase.

[0026] Figure 6 This is the total ion spectrum of a toothpaste sample using a C4 column with methanol and 0.1% formic acid water as the mobile phase. DETAILED DESCRIPTION

[0027] The following will describe in detail a number of specific embodiments of the present invention. It should be noted that these embodiments are merely examples, intended to more clearly illustrate the technical concept and implementation of the present invention, and should not be construed as limiting the scope of protection of the present invention. In practical applications, they can be adjusted and changed according to specific needs.

[0028] In the process of implementing the present invention, the specific operating conditions, parameters, etc. of each step can be reasonably changed within a certain range. As long as the purpose and technical effects of the present invention can be achieved, these changed implementation methods all fall within the protection scope of the present invention. The specific numerical values ​​given in the following examples are only for illustration and are not the only limitation on the parameter range.

[0029] Example 1 Elution effect of pentafluorophenyl column: Example 1.1 Pentafluorophenyl column gradient elution: Take 7 kinds of organic fluoride standards and directly dissolve them in methanol solution to obtain an organic fluorine source standard solution. The organic fluorine source standard solution is analyzed by the machine. The liquid chromatography conditions are set as follows: mobile phase A uses methanol, mobile phase B uses 0.1% formic acid water for gradient elution, the chromatographic column is a pentafluorophenyl column, and gradient elution is used. The elution conditions are as follows: 0-0.5 min, methanol 85%, 0.5-2 min, methanol 100%, hold for 2 min, 4.1-6 min, methanol 85%, and the ion spectrum of the test solution is as follows: Figure 1 As shown, Figure 1 NO.1 in the figure represents 3-pyridinemethanol hydrogen fluoride, NO.5 represents hexadecylamine, NO.6 represents diketafur, and NO.7 represents octadecylamine. It can be seen that bis(hydroxyethylaminopropylhydroxyethylhexadecylamine, bis(hydroxyethylaminopropylhydroxyethyloleylamine) and bis(hydroxyethylaminopropylhydroxyethyloctadecylamine) cannot be eluted under the liquid chromatography conditions.

[0030] Example 1.2 Pentafluorophenyl column gradient elution: The organic fluoride standard was directly dissolved in methanol solution to obtain an organic fluoride source standard solution, and the organic fluoride source standard solution was analyzed on a liquid chromatography machine, wherein the liquid chromatography conditions were set as follows: methanol was used as mobile phase A, 0.1% ammonium formate acetate solution (5-10 Mmol / L) was used as mobile phase B, gradient elution was used, and the chromatographic column was Athena C18. Gradient elution was used, and the elution conditions were as follows: 0-0.5 min, 85% methanol, 0.5-2 min, 100% methanol, maintained for 2 min, 4.1-6 min, 85% methanol, and the ion spectrum of the solution to be tested was obtained. The liquid chromatography conditions can elute 7 kinds of organic fluorides, but the peaks of bis(hydroxyethylaminopropylhydroxyethylhexadecylamine, bis(hydroxyethylaminopropylhydroxyethyloleylamine) and bis(hydroxyethylaminopropylhydroxyethyloctadecylamine) were obviously tailed, which was not conducive to quantitative analysis. Figure 2 It is the ion chromatogram of NO.2~NO.4, NO.2 represents bis(hydroxyethylaminopropylhydroxyethylhexadecylamine), NO.3 represents bis(hydroxyethylaminopropylhydroxyethyloleylamine), and NO.4 represents bis(hydroxyethylaminopropylhydroxyethyloctadecylamine.

[0031] Example 1.3 Pentafluorophenyl column gradient elution: The organic fluoride standard was directly dissolved in methanol solution to obtain an organic fluorine source standard solution, and the organic fluorine source standard solution was analyzed on a liquid chromatography machine, wherein the liquid chromatography conditions were set as follows: acetonitrile was used as mobile phase A, 0.1% ammonium formic acid acetate solution (5-10 Mmol / L) was used as mobile phase B, gradient elution was used, the chromatographic column was Athena C18, and gradient elution was used. The elution conditions were as follows: 0-0.5 min, 85% methanol, 0.5-2 min, 100% methanol, maintained for 2 min, 4.1-6 min, 85% methanol, and the ion spectrum of the solution to be tested was obtained. The liquid chromatography conditions could only elute 3-pyridinemethanol hydrogen fluoride, and the other 6 organic fluorides could not be eluted, indicating that acetonitrile was not suitable for mass spectrometry ionization.

[0032] Example 2 Elution effect of C4 chromatographic column: Example 2.1 C4 chromatographic column gradient elution: Seven kinds of organic fluoride standards were directly dissolved in methanol solution to obtain an organic fluorine source standard solution, and the organic fluorine source standard solution was analyzed by a liquid chromatography, wherein the liquid chromatography conditions were set as follows: methanol was used as mobile phase A, 0.1% ammonium formate acetate (5-10Mmol / L) as mobile phase B for gradient elution, the chromatographic column was Athena C4, the specification size was 2.1×100 mm, 5µm, gradient elution was used, and the elution conditions were: 0-0.5 min methanol 80%; 0.5-4 min, methanol 80%-95%; 4.1-5.5min, methanol 80%, and the total ion spectrum of the solution to be tested was obtained as shown below: Figure 3 The ion spectra of each organic fluoride extracted are shown in Figure 4 As shown, NO.1 represents 3-pyridinemethanol hydrogen fluoride, NO.2 represents bis(hydroxyethylaminopropylhydroxyethylhexadecylamine), NO.3 represents bis(hydroxyethylaminopropylhydroxyethyloleylamine), NO.4 represents bis(hydroxyethylaminopropylhydroxyethyloctadecylamine), NO.5 represents hexadecylamine, NO.6 represents diketafol, and NO.7 represents octadecylamine. It can be seen that seven kinds of organic fluorides can be eluted under this condition, but the ion peaks of bis(hydroxyethylaminopropylhydroxyethylhexadecylamine and bis(hydroxyethylaminopropylhydroxyethyloleylamine) are bifurcated peaks.

[0033] Example 2.2 C4 chromatographic column gradient elution: Seven kinds of organic fluoride standards were directly dissolved in methanol solution to obtain an organic fluorine source standard solution, and the organic fluorine source standard solution was analyzed by the liquid chromatography, wherein the liquid chromatography conditions were set as follows: methanol was used as mobile phase A, 0.1% formic acid water was used as mobile phase B for gradient elution, the chromatographic column was Athena C4, the specification size was 2.1×100 mm, 5µm, gradient elution was used, and the elution conditions were: 0~0.5 min methanol 80%; 0.5-4 min, methanol 80%~95%; 4.1~5.5 min, methanol 80%, and the total ion spectrum of the solution to be tested was obtained as shown in the figure. Figure 5 As shown, NO.1 represents 3-pyridinemethanol hydrogen fluoride, NO.2 represents bis(hydroxyethylaminopropylhydroxyethylhexadecylamine), NO.3 represents bis(hydroxyethylaminopropylhydroxyethyloleylamine), NO.4 represents bis(hydroxyethylaminopropylhydroxyethyloctadecylamine), NO.5 represents hexadecylamine, NO.6 represents diketafur, and NO.7 represents octadecylamine. It can be seen that the conditions can elute 7 kinds of organic fluorides, and the peak shape of the target peak of each organic fluoride is better, which is more conducive to the quantitative analysis of each organic fluoride.

[0034] Example 2.3 C4 chromatographic column gradient elution: Dissolve the toothpaste to be tested in 30 mL of pure water, ultrasonicate for 10-20 min, and dilute to 50 ml. Take 200 µ1-1 mL and dilute to 10 ml with ultrapure water. After purification is completed by activating the HLB solid phase extraction column with 1-5 mL of methanol and water respectively, take 1-3 ml of the dilution to purify the column. Elute with 3-5 mL of purified water, and finally elute and collect with 3-5 mL of methanol, dilute to 10 ml with methanol, mix well, and analyze on the machine after passing through the membrane. The solution to be tested is analyzed on the machine, and the liquid chromatography conditions are set as follows: methanol is used as mobile phase A, and 0.1% formic acid water is used as mobile phase B for gradient elution. The chromatographic column is Athena C4, with a specification size of 2.1×100 mm, 5µm, and gradient elution is used. The elution conditions are: 0~0.5 min methanol 80%; 0.5~4 min, methanol 80%~95%; 4.1~5.5 min, methanol 80%, and the total ion spectrum of the solution to be tested is obtained as shown below. Figure 6 shown.

[0035] Example 3 Matrix Effect Taking toothpaste samples as an example, equal amounts of organic fluoride were respectively diluted with methanol solvent and methanol solvent with a certain amount of matrix (matching the sample amount and the volume of the column sample purification) added, and more than two parallel determinations were performed. The calibration curve of the standard sample diluted with methanol solution was used for calibration respectively. The results were taken as the average value of the parallel samples, and the matrix effect determination results were obtained as shown in Table 3 below: Table 3 Matrix effect test results (toothpaste samples) .

[0036] It can be seen that except hexadecylamine, diketafur and octadecylamine, the other four organic fluorides have significant matrix inhibition effects.

[0037] Example 4 Effect of Solid Phase Extraction Column on Recovery Rate In order to reduce the matrix effect, the applicant team selected C4 column, C18 column and HLB column to compare the purification effect and recovery rate. The toothpaste sample without fluoride was used as blank, and 7 kinds of organic fluorides with certain concentrations were added as test objects to examine the recovery rate. The results are shown in Tables 4 and 5.

[0038] Table 4 Recovery rate of methanol elution (%) .

[0039] Table 5 Recovery rate when eluted with 0.1% formic acid and methanol (%) .

[0040] As can be seen from Tables 4 and 5, when eluted with methanol, the recovery rates of 3-pyridinemethanol hydrofluoride, hexadecylamine, diketafur and octadecylamine by C18 solid phase extraction column were all low, but the recovery rate of diketafur was significantly improved when eluted with formic acid methanol. Compared with methanol, formic acid methanol as an eluent had no significant effect on the recovery rates of C4 and HLB columns, but the recovery rate of 3-pyridinemethanol hydrofluoride by C4 column was low, and the recovery rate of each target compound could be achieved above 60% when HLB column was eluted with methanol.

[0041] Those skilled in the art should understand that the technical features of the above embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0042] The above embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the present application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached claims.

Claims

1. A method for rapidly identifying organic fluorides in oral care products and their raw materials, characterized in that: The following steps are involved: Get the object to be tested; The object to be tested is ultrasonically dissolved with water to obtain a first solution, and the first solution is pre-treated twice to obtain a solution to be tested, wherein when the object to be tested is an oral care product raw material, mouthwash and spray, the first solution is diluted with water and methanol step by step to obtain a solution to be tested; when the object to be tested is a toothpaste-type oral care product, the first solution is diluted with water to obtain an analysis solution, and a solid phase extraction column is activated with methanol and water in sequence, and the analysis solution is purified through the column to obtain a purified solution, which is washed with purified water and then eluted with methanol to collect the solution to be tested; The solution to be tested is detected by liquid chromatography-tandem mass spectrometry in MRM mode to obtain a chromatogram, wherein the chromatographic column of the liquid chromatography is an Athena C4 or C8 analytical column, wherein when the Athena C4 analytical column is used, the mobile phase A is methanol, and the mobile phase B is 0.1% formic acid water, and when the C8 analytical column is used, the mobile phase A is methanol, and the mobile phase B is a 5-10 Mmol / L ammonium acetate solution containing 0.1% formic acid, and the elution method is gradient elution; The quantitative or qualitative analysis of organic fluoride can be performed through qualitative and quantitative ion pairs.

2. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: The object to be detected is any one or a combination of seven organic fluorides, namely, 3-pyridinemethanol hydrogen fluoride, bishydroxyethylaminopropylhydroxyethylhexadecylamine, bishydroxyethylaminopropylhydroxyethyloleylamine, bishydroxyethylaminopropylhydroxyethyloctadecylamine, hexadecylamine, diketafur and octadecylamine.

3. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: The flow rate was set at 0.3~0.5 ml / min, the column temperature was 35℃~50℃, and the elution conditions of the gradient elution were: 0~0.5 min, methanol 80%; 0.5~4 min, methanol 80%~95%; 4.1~5.5 min, methanol 80%.

4. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When it is necessary to qualitatively identify organic fluorides, take an organic fluoride standard and dissolve it in methanol solution to obtain an organic fluorine source standard solution. The organic fluorine source standard solution is tested under the same liquid chromatography and mass spectrometry conditions. The retention time of the chromatogram of the test solution is compared with the retention time of the chromatogram of the organic fluorine source standard solution, and the characteristic ions are compared with the characteristic ions in the organic fluorine source standard solution of corresponding concentration for qualitative identification. If the relative deviation of the retention time is not greater than 5%, and the abundance of the characteristic ions in the test solution and the abundance of the characteristic ions in the organic fluorine source standard solution are within the allowable deviation, it is considered that the corresponding organic fluoride is identified.

5. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When it is necessary to quantitatively detect organic fluorides, an organic fluoride standard is dissolved in a methanol solution to obtain an organic fluorine source standard solution of different concentrations, the organic fluorine source standard solution is detected under the same chromatographic and mass spectrometric conditions, and a standard substance concentration-response intensity external standard method curve is drawn based on the detection results, wherein the standard substance concentration-response intensity external standard method curve records the relationship between the concentration of the organic fluoride and the response intensity, and the corresponding organic fluoride content is obtained based on the standard substance concentration-response intensity external standard method curve according to the response intensity of the solution to be tested in the liquid chromatograph, and the organic fluoride ion content is converted therein.

6. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 5, characterized in that: The concentration of the standard working solution of the organic fluorine source is 1~500 µg / L.

7. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When the objects to be tested are oral care product raw materials, mouthwashes and sprays, the first solution is diluted stepwise with water and methanol and then passed through a membrane to obtain a test solution, wherein the first solution is diluted with water until the target content in the sample is less than 10 ppm, and is diluted with methanol until the target content is within the linear range of 1-500 ppb.

8. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When the object to be tested is a toothpaste-type oral care product, the first solution is diluted and dissolved with purified water to obtain an analysis solution, 1-3 mL of the analysis solution is taken to pass through a column for purification, methanol and water with a volume ratio of 1 to 3 times the analysis solution are used in sequence for solid phase extraction of a small column, the analysis solution is taken to pass through a small column for purification, the solution is rinsed with purified water with a volume ratio of 1 to 3 times the analysis solution, the solution is eluted and collected with methanol with a volume ratio of 1 to 5 times the analysis solution, and the solution to be tested is obtained after constant volume with methanol.

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