Method for determining residual quantity of 1, 3-dioxolame and trioxane in contact POM material

Abstract

The invention discloses a method for measuring the residual quantity of 1, 3-dioxolame and trioxane in a contact POM material for medical equipment, which comprises the following steps: preparing a 1, 3-dioxolame standard stock solution, a trioxane standard stock solution, a 1, 3-dioxolame and trioxane mixed standard solution, a to-be-measured sample solution and a blank reagent solution; respectively injecting the mixed standard solution, the blank reagent solution and the to-be-detected sample solution into a gas chromatograph-mass spectrometer, detecting according to a set gas chromatograph-mass spectrometer condition, measuring a TIC spectrogram response value, and drawing a standard curve by taking the mass concentration of the mixed standard solution as an abscissa and the corresponding response value as an ordinate. And comparing the response value measured by the sample to be detected with the standard curve for quantification, and calculating the residual quantity of 1, 3-dioxolame and trioxane in the sample to be detected. The detection method has the characteristics of high efficiency, sensitivity, simplicity, convenience and good accuracy and repeatability.

Description

Technical Field

[0001] The present invention relates to the technical field of medical device detection, and particularly relates to a method for detecting the residual amounts of 1,3-dioxolane and trioxane. Background Art

[0002] With the increasing attention of people to medical health and the rapid development of the medical device industry, ensuring the safety of medical device contact materials has become one of the core tasks of the industry. Among them, the contact POM (polyoxymethylene) material used in medical devices is widely used in medical devices such as surgical instruments and syringes due to its excellent mechanical properties, wear resistance and chemical stability.

[0003] Some unreacted monomers or by-products may remain in the production process of POM materials, such as 1,3-dioxolane and trioxane. Medical devices are in direct contact with the human body and migrate into the body during the use by medical staff and patients. These residues are somewhat toxic.

[0004] Long-term contact may cause harm to human health. The presence of residues may trigger allergic reactions or other health problems. Therefore, various countries have strict limit requirements for residues in medical device materials, and these residues need to be accurately detected to ensure that they are within the safety limits, directly reducing the risk of patients and medical staff contacting harmful substances, ensuring the safety of medical devices, and thus effectively avoiding medical disputes, product recalls or legal lawsuits, etc. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for determining the residual amounts of 1,3-dioxolane and trioxane in contact POM materials, which has the characteristics of high efficiency, sensitivity and simplicity.

[0006] A method for detecting the residual amounts of 1,3-dioxolane and trioxane in contact POM materials, characterized by comprising the following steps:

[0007] A): Preparation of standard stock solutions:

[0008] Preparation of 1,3-dioxolane standard stock solution: Accurately weigh 0.0500 g of 1,3-dioxolane standard product, dissolve it with DMAC, and make up the volume to 50 mL, and store it in a refrigerator at 4°C;

[0009] Preparation of trioxane standard stock solution: Accurately weigh 0.0500 g of trioxane standard product, dissolve it with DMAC, and make up the volume to 50 mL, and store it in a refrigerator at 4°C;

[0010] Preparation of a series of mixed standard solutions: Pipette the above two standard stock solutions, dilute them with DMAC to prepare a series of mixed standard solutions with a concentration range of 0.05 μg / mL to 50 μg / mL, at least 5 concentrations;

[0011] B): Preparation of the sample solution to be measured: Weigh the POM material part of the medical device accurately to obtain 1.00 g, place it in a 20 mL headspace vial, add 5 mL of DMAC, quickly cover and seal it. Keep the headspace vial upright on the table and gently shake it evenly by making rapid circular motions on the horizontal tabletop with your hand, so that the solvent completely submerges the sample and is fully mixed. During the shaking process, the matrix solvent must not touch the gasket. If there is contact, it needs to be re-prepared. Place the sample vial in a constant temperature and humidity chamber at 37 °C for 24 h, let it stand and cool to room temperature, separate the solid and liquid for injection analysis, and thus obtain the sample solution to be measured;

[0012] C): Preparation of the blank reagent: Except for not adding the sample, the rest is prepared according to the preparation method of the sample solution to be measured.

[0013] D): Determination: Inject the series of mixed standard solutions, blank reagent solution, and sample solution to be measured into the gas chromatography - mass spectrometry (GC - MS) instrument respectively, and perform detection according to the set GC - MS conditions to obtain the TIC chromatogram response values. Take the mass concentration of the mixed standard solution as the abscissa and the corresponding response value as the ordinate to draw a standard curve. Compare the target compounds of the sample to be measured and the blank reagent solution to appear at the same retention time (±0.5%), and the mass - to - charge ratio of the corresponding mass spectrometry fragment ions and the mass spectrometry diagram of the standard product to qualitatively obtain the target analyte and measure the response value of the sample to be measured. Then compare the response value with the standard curve for quantification, and measure the contents X of 1,3 - dioxolane and trioxane in the sample to be measured. Calculate the residue amounts C of 1,3 - dioxolane and trioxane according to the following formula:

[0014]

[0015] C: Residue amount of 1,3 - dioxolane or trioxane in the sample, μg / g

[0016] X: Content of 1,3 - dioxolane or trioxane in the measured sample solution, μg / mL

[0017] V: Volume of the sample extraction solution, mL

[0018] M: Weight of the sample, g

[0019] The GC - MS conditions used in step D) are as follows:

[0020] Chromatographic column: VF - 624ms capillary column, 30.0 m long, 0.32 mm ID inner diameter, 1.80 μm film thickness;

[0021] Column flow rate: 2.5 mL / min, constant flow mode;

[0022] Vaporization temperature of the injection port: 200 °C;

[0023] Injection method: split injection, split ratio 1:1

[0024] Carrier gas: high-purity helium (purity greater than 99.999%);

[0025] Chromatographic column temperature program:

[0026] Detector: electron impact source (EI);

[0027] Solvent delay: 3 min;

[0028] Detector interface temperature: 250 °C;

[0029] Detector temperature: 250 °C;

[0030] Ion source temperature: 230 °C;

[0031] Quadrupole temperature: 150 °C;

[0032] The selected ion monitoring (SIM) scanning mode is adopted, and the scanning program is as follows:

[0033] The standard curve described in step D): Respectively pipette 1 μL of the at least 5 concentration standard working solutions, and inject them into the gas chromatograph-mass spectrometer respectively to obtain the response values of 1,3-dioxolane and trioxane in the standard working solutions. Taking the response value of the corresponding quantitative ion as the ordinate and the mass concentration of the standard working solution as the abscissa, draw the standard curve.

[0034] The standard curve of 1,3-dioxolane is Y = 44785.295385X + 9143.772735, in the range of (0.05 - 50) μg / mL, the correlation coefficient r 2 = 0.99943448 (n = 8)

[0035] The standard curve of trioxane is Y = 11492.668215X + 3689.625743, in the range of (0.05 - 50) μg / mL, the correlation coefficient r 2 = 0.99943448 (n = 8)

[0036] Y is the response value, X is the content of 1,3-dioxolane or trioxane in the measured sample solution, μg / mL

[0037] The at least 5 concentrations described in step A), the concentrations can be:

[0038] The present invention provides a method for determining the residues of 1,3-dioxolane and trioxane in a contact POM material for medical devices. Through research and analysis, it is found that DMAC (N,N-dimethylacetamide) is selected as the extraction solvent because of its high selectivity for target compounds, low matrix interference, low toxicity and environmental friendliness. The extraction conditions are optimized to extract at a constant temperature of 37 °C for 24 h to balance the extraction efficiency and stability.

[0039] The present invention obtains the correlation between different extraction solvents, times, temperatures and the measurement results through research, and optimizes the instrumental method. The present invention has the advantages of high recovery rate, good precision and being suitable for the efficient extraction of target compounds in complex matrices.

[0040] The detection limits of the detection method proposed by the present invention are: the detection limits of 1,3-dioxolane and trioxane are 0.025 mg / kg and 0.025 mg / kg respectively, and the RSD (%) is 3.83%, indicating that the present invention has a relatively stable matrix effect and high sensitivity. The recovery rate range of 1,3-dioxolane is 91.56% - 102.71%, and the repeatability RSD (%) range is: 2.06% - 3.29%. The low recovery rates of trioxane are 84.89% - 102.62% respectively, and the repeatability RSD (%) are 2.05% - 4.39% respectively. It shows that the method provided by the present invention is simple to operate, has good selectivity, good measurement accuracy and repeatability, and the detection limits and recovery rates meet the detection requirements.

[0041] The present invention can be used to solve problems such as product quality self-inspection of production enterprises, risk detection and administrative supervision of government departments and the medical device industry, and personal safety guarantee of medical staff and patients. It can effectively protect public health, standardize the market order, promote industrial upgrading, enhance international competitiveness, and enhance consumers' confidence in domestic medical devices. Description of the Drawings

[0042] Figure 1 is the total ion chromatogram of selected ions

[0043] Figure 2 is the mass spectrum of 1,3-dioxolane

[0044] Figure 3 is the mass spectrum of trioxane Detailed Embodiments

[0045] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below with reference to the relevant drawings. The preferred embodiments of the present invention are given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0046] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used in the present invention includes any and all combinations of one or more of the related listed items

[0047] Example 1:

[0048] 1. Experimental instruments, reagents and materials:

[0049] 1.1 Chloroform: Chromatographically pure

[0050] 1.2 N,N-Dimethylacetamide (DMAC): HPLC

[0051] 1.3 N,N-Dimethylformamide (DMF): Chromatographically pure

[0052] 1.4 Acetone: HPLC

[0053] 1.5 Glass headspace vial: 20 mL

[0054] 1.6 Volumetric flasks: 10 mL, 50 mL, 100 mL, 250 mL

[0055] 1.7 Microliter glass syringes: 1000 μL, 500 μL, 250 μL, 100 μL, 50 μL, 5 μL

[0056] 1.8 Glass pipettes: 25 mL, 10 mL, 5 mL, 1 mL

[0057] 1.9 Glass sample vial: 1 mL

[0058] 1.10 Glass dropper

[0059] 1.11 Glass beaker

[0060] 1.12 1,3-Dioxolane: Purity: 99.63% Source: Stanford Analytical Chemicals Inc LOT NO.: PW230417-30

[0061] Trioxane reference material: Purity: 99.72% Source: Stanford Analytical Chemicals Inc LOT NO.: ISE-392841

[0062] 1.14 Triple quadrupole gas chromatography-mass spectrometry

[0063] 1.15 ME5 ultra-micro electronic balance

[0064] 1.16WNB400 Constant temperature and humidity chamber

[0065] 1.17ML204T electronic balance

[0066] 1.18HCP153 Constant temperature and humidity chamber

[0067] 1.19KQ-300VDE dual frequency CNC ultrasonic cleaner

[0068] 2. Operation steps

[0069] A) Preparation of standard stock solution

[0070] 1,3-Dioxolane standard stock solution: Accurately weigh 0.04940 g of 1,3-dioxolane standard, dissolve it in DMAC, make up to 50 mL, and store in a 4°C refrigerator;

[0071] Trioxane standard stock solution: accurately weigh 0.04791 g of trioxane standard, dissolve it in DMAC, make up to 50 mL, and store in a 4°C refrigerator;

[0072] Prepare a series of mixed standard solutions: pipette an appropriate amount of standard stock solution, add DMAC to dilute and prepare a series of mixed standard solutions with a concentration range of 0.05μg / mL to 50μg / mL, at least 5 concentrations. In this example, 8 concentrations are used.

[0073] B): Preparation of samples to be tested

[0074] Cut the sample "clip of the continuous clip applicator (POM material)" to be tested into pieces smaller than 1 cm, accurately weigh 1.00 g, place it in a 20 mL headspace injection bottle, add 5 mL DMAC, quickly cover and seal, keep the headspace injection bottle upright on the table, and gently shake it on the horizontal table in a quick circular motion to mix it, so that the solvent completely immerses the sample and mixes it thoroughly. The solvent must not contact the sealing pad during the rotation. If it does, it needs to be re-prepared. Place the above sample bottle in a 37°C constant temperature and humidity chamber for 24 hours, let it stand and cool to room temperature, separate the solid and liquid for injection and analysis, and the sample to be tested is obtained;

[0075] C): Prepare blank sample: except that no sample to be tested is added, other steps are the same as the "preparation of sample to be tested" method.

[0076] Gas chromatography-mass spectrometry conditions:

[0077] Chromatographic column: VF-624ms capillary column, length 30.0m, inner diameter 0.32mm ID, film thickness 1.80μm;

[0078] Column flow rate: 2.5 mL / min, constant flow mode;

[0079] Vaporization temperature of the injection port: 200 °C;

[0080] Injection method: split injection, split ratio 1:1

[0081] Carrier gas: high-purity helium (purity greater than 99.999%);

[0082] Chromatographic column temperature program:

[0083] Detector: electron impact source (EI);

[0084] Solvent delay: 3 min;

[0085] Detector interface temperature: 250 °C;

[0086] Detector temperature: 250 °C;

[0087] Ion source temperature: 230 °C;

[0088] Quadrupole temperature: 150 °C;

[0089] The selected ion monitoring (SIM) scan mode is adopted, and the scan program is as follows:

[0090] C): Content determination and calculation

[0091] Inject the series of mixed standard solutions, blank reagent solutions, and test sample solutions into the gas chromatography-mass spectrometry instrument respectively, and perform detection according to the set gas chromatography-mass spectrometry conditions to obtain the TIC chromatogram response values. Take the mass concentration of the mixed standard solution as the abscissa and the corresponding response value as the ordinate to plot the standard curve. Compare that the target compounds of the test sample and the blank reagent solution appear at the same retention time (±0.5%), and the mass-to-charge ratio of the corresponding mass spectrometry fragment ions with the mass spectrometry diagram of the standard product to qualitatively obtain the target analyte and measure the response value of the test product. Then compare the response value with the standard curve for quantification, measure the contents X of 1,3-dioxolane and trioxane in the test sample, and calculate the residues C of 1,3-dioxolane and trioxane according to the following formula. The technical formula is as follows:

[0092]

[0093] C: Residue of 1,3-dioxolane or trioxane in the sample, μg / g

[0094] X: Content of 1,3-dioxolane or trioxane in the measured sample solution, μg / mL

[0095] V: Volume of the sample extraction solution, mL

[0096] M: Specimen weight, g

[0097] Drawing of the standard curve:

[0098] Inject 1 μL of a series of standard working solutions into the gas chromatograph - mass spectrometer to obtain the response values of 1,3 - dioxolane and trioxymethylene in the standard working solutions. Plot the standard curve with the response value of the corresponding quantitative ion as the ordinate and the mass concentration of the standard working solution as the abscissa.

[0099] Table 4 1,3 - Dioxolane standard

[0100] The standard curve of 1,3 - dioxolane is y = 44785.295385x + 9143.772735. In the range of (0.0984 - 49.2172) μg / mL, with an injection volume of 1 μL, it shows a good linear relationship, and the correlation coefficient r 2 = 0.99943448 (n = 8).

[0101] Table 5 Trioxymethylene standard curve

[0102] The standard curve of trioxymethylene is y = 11492.668215x + 3689.625743. In the range of (0.0956 - 47.7759) μg / mL, with an injection volume of 1 μL, it shows a good linear relationship, and the correlation coefficient r 2 = 0.99908496 (n = 8).

[0103] Y is the response value, and X is the content of 1,3 - dioxolane or trioxane in the test sample solution, μg / mL

[0104] Table 6 Determination results of reagent blank solution and test solution

[0105] According to the above method, the test sample in this case was detected, and the test result was not detected.

[0106] 4. Methodological verification

[0107] 4.1 Method detection limit

[0108] Take a mixed standard working solution with a concentration of about 0.1 μg / mL and dilute it until the peak height is 3 times the signal - to - noise ratio. The corresponding concentration at this time is the detection limit. The results are shown in Table 7.

[0109] Table 7 Method detection limit

[0110] It can be seen from the results that when the sampling amount is 1 g, the injection volume is 1 μL, the split ratio is 1:1, and the detection limits of 1,3-dioxolane and trioxane by this method are 0.025 mg / kg and 0.025 mg / kg respectively.

[0111] 4.2 Instrument precision test

[0112] Take about 30 μg / mL of the mixed standard working solution and determine it according to the instrument method. Inject 1 μL into the gas chromatograph-mass spectrometer and inject continuously six times. Record the response values of 1,3-dioxolane and trioxane respectively. The results are shown in Table 8.

[0113] Table 8 Results of precision test

[0114] It can be seen from the results that when the mixed standard solution is injected continuously six times, the RSD(%) values of the precision of 1,3-dioxolane and trioxane are 2.06% and 2.09% respectively (n = 6), showing good precision.

[0115] 4.3 Matrix effect stability test

[0116] Take the negative test sample solution and add a certain amount of the mixed standard solution for pretreatment according to the method in

[0072] B): Preparation method of test samples. Take the supernatant and analyze it by gas chromatography-mass spectrometer according to the gas chromatography-mass spectrometry determination conditions. Set the liquid-taking position of the instrument injection needle at a height of 1 mL. Between 0 h and 48 h, inject 1 μL into the gas chromatograph-mass spectrometer, record the time and response value. The results are shown in Table 9.

[0117] Table 9 Results of matrix effect stability test

[0118] It can be seen from the results that the test sample solution after spiking has good stability within 48 hours, and the RSD(%) is 3.83%. This method has a relatively stable matrix effect.

[0119] 4.4 Recovery determination - Repeatability, accuracy

[0120] 4.4.1 Preparation of recovery test samples:

[0121] a. Take parts of the above-mentioned POM material to be tested, and accurately weigh ①1.0217 g, ②1.0114 g, ③1.0095 g, ④1.0122 g, ⑤1.0340 g, ⑥1.0071 g. Place them in a 20 mL headspace vial, then add 250 μL of 1,3-dioxolane standard solution (concentration: 98.4344 μg / mL) and 250 μL of trioxane standard stock solution (concentration: 95.5518 μg / mL) respectively. Add DMAC to make the volume up to 5.0 mL, quickly cover and seal it. Prepare the others according to the sample treatment method.

[0122] b. Take parts of the above-mentioned POM material to be tested, and accurately weigh ①1.0248 g, ②0.9890 g, ③0.9976 g, ④1.0256 g, ⑤1.0175 g, ⑥1.0333 g. Place them in a 20 mL headspace vial, then add 125 μL of 1,3-dioxolane standard solution (concentration: 49.2172 μg / mL) and 125 μL of trioxane standard stock solution (concentration: 47.7759 μg / mL) respectively. Add DMAC to make the volume up to 5.0 mL, quickly cover and seal it. Treat it in the same way as in 2.2.

[0123] c. Take parts of the above-mentioned POM material to be tested, and accurately weigh ①1.0089 g, ②1.0166 g, ③1.0339 g, ④1.0251 g, ⑤1.096 g, ⑥1.0281 g. Place them in a 20 mL headspace vial, then add 25 μL of 1,3-dioxolane standard solution (concentration: 49.2172 μg / mL) and 25 μL of trioxane standard stock solution (concentration: 47.7759 μg / mL) respectively. Add DMAC to make the volume up to 5.0 mL, quickly cover and seal it.

[0124] Take the above solutions and measure them under the same chromatographic conditions as the standard working solution and the test sample solution. Quantify them by the standard curve method and calculate the recovery rate. Calculate the repeatability based on the measurement results of 6 recovery samples at the same addition level. The results are shown in Table 10 - Table 15.

[0125] 4.4.2 Data and Results

[0126] Table 10 Determination Results of the Recovery Rate of 1,3-Dioxolane at a Low Level a

[0127] Table 11 Determination Results of the Recovery Rate of 1,3-Dioxolane at a Medium Level b

[0128] Table 12 Determination Results of the Recovery Rate of 1,3-Dioxolane at a High Level c

[0129] Table 13 Determination Results of the Recovery Rate of Trioxane at a Low Level a

[0130] Table 14 Determination Results of the Recovery Rate of Trioxane at a Medium Level b

[0131] Table 15 Determination Results of the Recovery Rate of Trioxane at a High Level c

[0132] It can be seen from the results that the recovery rates of 1,3-dioxolane at low, medium, and high levels are 91.56%, 102.71%, and 100.28% respectively, and the repeatability RSD(%) of 6 parallel tests at each addition level is 2.53%, 3.29%, and 2.06% respectively. The recovery rates of trioxane at low, medium, and high levels are 84.89%, 92.65%, and 102.62% respectively, and the repeatability RSD(%) of 6 parallel tests at each addition level is 4.69%, 2.56%, and 2.05% respectively. It shows that the accuracy and repeatability of this method are good.

[0133] Example 2:

[0134] The baby umbilical cord clip (POM material) was cut into sections about 1 cm in length and mixed evenly. The test solution and blank solution were prepared under the method conditions in Example 1, and the instrument conditions were used for determination. The results were calculated using formula (1), and the determination results are shown in Table 16.

[0135] Table 16 Determination Results of 1,3-Dioxolane and Trioxane in the Baby Umbilical Cord Clip

[0136] The inspection results show that there is about 0.3 mg / g of 1,3-dioxolane and about 0.26 mg / g of trioxane in the tested sample of the baby umbilical cord clip.

[0137] Example 3:

[0138] For the medical electronic infusion pump (POM material), the adapter (POM material) was taken, cut into sections about 1 cm in length and mixed evenly. The test solution and blank solution were prepared under the method conditions in Example 1, and the instrument conditions were used for determination. The results were calculated using formula (1), and the determination results are shown in Table 17.

[0139] Table 17 Determination Results of 1,3-Dioxolane and Trioxane in the Adapter of the Medical Electronic Infusion Pump

[0140] The inspection results show that there is about 0.55 mg / g of 1,3-dioxolane in the tested sample of the adapter of the medical electronic infusion pump, and trioxane was not detected.

[0141] Example 4:

[0142] Medical surgical forceps (POM material), take the head (POM material), cut it into sections about 1 cm long and mix evenly. Prepare the test sample solution and reagent blank solution and conduct the determination under the method conditions in Example 1 and the instrument conditions. Calculate the results using formula (1), and the determination results are shown in Table 18.

[0143] Table 18 Determination results of 1,3-dioxolane and trioxane in the head of medical surgical forceps (POM material)

[0144] The inspection results show that there is about 0.265 mg / g of trioxane in the head of the medical surgical forceps to be inspected, and 1,3-dioxolane is not detected.

[0145] Through the above repeatability experiments, it can be seen that the detection method of the present application has good repeatability for the determination method of the residual amounts of 1,3-dioxolane and trioxane in the contact POM material for medical devices.

[0146] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, 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, it should be considered as the scope described in this specification.

[0147] The above-described embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A detection method for the residual amounts of 1,3-dioxolane and trioxane in a contact POM material, characterized in that, It includes the following steps: A): Preparation of standard stock solutions: Preparation of 1,3-dioxolane standard stock solution: Accurately weigh 0.0500 g of 1,3-dioxolane standard sample, dissolve it in DMAC, make up the volume to 50 mL, and store it in a refrigerator at 4°C; Preparation of trioxane standard stock solution: Accurately weigh 0.0500 g of trioxane standard sample, dissolve it in DMAC, make up the volume to 50 mL, and store it in a refrigerator at 4°C; Preparation of a series of mixed standard solutions: Weigh the above two standard stock solutions, dilute and prepare a series of mixed standard solutions with a concentration range of 0.05 μg / mL to 50 μg / mL with DMAC, including at least 5 concentrations; B): Preparation of the sample solution to be measured: Weigh the POM material part in the medical device, accurately weigh 1.00 g, place it in a 20 mL headspace vial, add 5 mL of DMAC, quickly cover and seal it, keep the headspace vial upright on the table, and gently shake it evenly by making a rapid circular rotation on the horizontal table with your hand to completely immerse the sample in the solvent for full mixing. During the rotation process, the solvent should not touch the gasket. If there is contact, it needs to be re-prepared. Place the sample vial in a constant temperature and humidity box at 37°C for 24 h, let it stand and cool to room temperature, separate the solid and liquid for injection analysis, and the sample solution to be measured is obtained; C): Preparation of blank reagent solution: Except for not adding the sample, it is prepared in the same way as the preparation method of the sample solution to be measured. D) Determination: Inject the series of mixed standard solutions, blank reagent solution, and sample solution to be measured into a gas chromatography-mass spectrometry (GC-MS) instrument respectively, and perform detection according to the set GC-MS conditions. Measure the TIC chromatogram response value. Take the mass concentration of the mixed standard solution as the abscissa and the corresponding response value as the ordinate to draw a standard curve. Compare the target compounds in the sample solution to be measured and the blank reagent solution to appear at the same retention time (±0.5%), and the mass-to-charge ratio of the corresponding mass spectrometry fragment ions with the mass spectrometry diagram of the standard sample to qualitatively obtain the target analyte. Measure the response value and compare it with the standard curve for quantification, and measure the residual contents X of 1,3-dioxolane and trioxane in the sample to be measured. Calculate the residual amounts C of 1,3-dioxolane and trioxane according to the following formula. The technical formula is as follows: C: Residual amount of 1,3-dioxolane or trioxane in the sample, μg / g X: Content of 1,3-dioxolane or trioxane in the measured sample solution, μg / mL V: Volume of the sample extraction solution, mL M: Weight of the sample, g.

2. The detection method according to claim 1, wherein: The GC-MS conditions in step D) are as follows: Chromatographic column: VF-624ms capillary column, 30.0 m long, 0.32 mm ID inner diameter, 1.80 μm film thickness; Column flow rate: 2.5 mL / min, constant flow mode; Injector vaporization temperature: 200°C; Injection mode: Split injection, split ratio 1:1 Carrier gas: High-purity helium (purity greater than 99.999%); Chromatographic column temperature program: Detector: Electron impact ionization source (EI); Solvent delay: 3 min; Detector interface temperature: 250°C; Detector temperature: 250°C; Ion source temperature: 230°C; Quadrupole temperature: 150°C; The selected ion monitoring (SIM) scan mode is adopted, and the scanning program is as follows:

3. The detection method according to claim 2, wherein: The specific standard curve described in step D) is as follows: The standard curve of 1,3-dioxolane is Y = 44785.295385X + 9143.772735, in the range of (0.05 - 50) μg / mL, the correlation coefficient r 2 = 0.99943448 (n = 8), and the detection limit is: 0.025 mg / kg The standard curve of trioxane is Y = 11492.668215X + 3689.625743, in the range of (0.05 - 50) μg / mL, the correlation coefficient r 2 = 0.99943448 (n = 8), and the detection limit is: 0.025 mg / kg Y is the response value, and X is the content of 1,3-dioxolane or trioxane in the test sample solution, μg / mL.

4. The method according to any one of claims 1 to 3, characterized in that: Not less than 5 concentrations described in step A) for preparing the series of standard solutions, and the concentrations can be:

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