Method for detecting migration degree of cyclosiloxane in paper package presswork

Abstract

The invention provides a method for detecting the migration degree of cyclosiloxane in a paper package printed matter, which comprises the following steps: carrying out a migration test on a to-be-detected paper package printed matter and a dry simulant to obtain a migrated dry simulant; preparing a standard working solution, preparing a paper package printed matter to be detected into a paper package printed matter sample solution, and preparing the obtained migrated dry simulant into a dry simulant sample solution; the standard working solution, the paper package printed matter sample solution and the dry simulant sample solution comprise internal standard substances; detecting cyclosiloxane substances in the standard working solution, the paper package printed matter sample solution and the dry simulant sample solution by adopting a headspace-gas chromatography / mass spectrometer; the migration volume and the migration rate are obtained. According to the method for detecting the migration degree of the cyclosiloxane substance in the paper package printed matter to the dry simulant by adopting the headspace-gas chromatography / mass spectrometer and the optimized conditions, the sensitivity is high, the recovery rate is high, and the precision is high.

Description

Technical Field

[0001] The present application belongs to the technical field of packaging printed matter detection, and in particular, relates to a method for detecting the degree of migration of cyclosiloxane in paper packaging printed matter. Background Art

[0002] Cyclosiloxane is a compound obtained by separation and distillation based on the product obtained by hydrolysis synthesis process of dimethyldichlorosilane. As an important intermediate, it can be used to prepare silicone polymers such as silicone oil. According to the harmonized classification and labeling (ATP15) approved by the European Union, typical cyclosiloxanes such as "octamethylcyclotetrasiloxane", "decamethylcyclopentasiloxane" and "dodecamethylcyclohexasiloxane" are suspected of destroying fertility, are highly toxic to aquatic organisms and have long-lasting effects. They have been listed as substances of high concern in the European Union. The European Commission (EU) Amendment No. 2018 / 35 and the international ecological textile standards have set limit requirements for related products. In the production process of paper packaging and printing, such substances may be used in the water-soluble inks and varnishes used, mainly for defoaming, smoothing, and changing the surface tension. When such paper packaging and printing are in direct or indirect contact with food, if the residual cyclosiloxane substances in the printed matter migrate into the food, it may affect the flavor quality of the food and bring risks to the health of consumers.

[0003] In order to detect the migration of cyclosiloxanes in paper packaging and printed materials, it is necessary to establish a targeted detection method. At present, relevant national and industry standards and reports mainly use gas chromatography, gas chromatography / mass spectrometry combined with liquid phase extraction and other methods to detect and analyze cyclosiloxane substances in related products. However, there are currently the following problems: 1. No attention is paid to paper packaging and printed materials: the main focus is on analysis objects such as silicone rubber, silicone pacifiers, medicinal plugs and groundwater; 2. The research on the migration of dry simulants is blank: it mainly focuses on the use of water, ethanol, n-hexane, acetic acid, etc. as simulants, and no detection methods for the migration of cyclosiloxane substances into dry simulants have been reported; 3. The influence of the paper matrix is ​​not fully considered: the influence of the paper matrix on the balance and signal intensity is not fully considered.

[0004] Therefore, it is necessary to develop a detection method to detect the migration amount of cyclosiloxane substances in paper packaging printed materials. Summary of the invention

[0005] Based on the above-mentioned defects of the prior art, the present application proposes for the first time a method for detecting the degree of migration of cyclosiloxanes in paper packaging printed materials into dry simulants. A headspace-gas chromatography / mass spectrometer and optimized conditions are used to detect the content of cyclosiloxanes in the sample to obtain the degree of migration of cyclosiloxanes in paper packaging printed materials into dry simulants, and a matrix calibrant, a blank paper matrix and an internal standard are added to calibrate the detection signal. The detection method and conditions of the present application have high sensitivity, high recovery rate and precision.

[0006] The first aspect of the present application provides a method for detecting the migration degree of cyclosiloxane in paper packaging printed matter, characterized in that the method comprises the following steps:

[0007] 1) Carry out migration test on the paper packaging printed matter and dry simulant to obtain the dry simulant after migration.

[0008] 2) preparing a standard working solution, preparing a paper packaging printed product sample solution with the paper packaging printed product to be tested, and preparing a dry simulant sample solution with the migrated dry simulant obtained in S1); the standard working solution, the paper packaging printed product sample solution, and the dry simulant sample solution include an internal standard and a solvent.

[0009] 3) Using headspace-gas chromatography / mass spectrometry to detect the cyclosiloxane in the standard working solution, the paper packaging printed matter sample solution and the dry simulant sample solution; using the standard working curve, the content of the cyclosiloxane in the paper packaging printed matter sample solution and the dry simulant sample solution is obtained, and the migration amount and mobility are obtained.

[0010] The second aspect of the present application provides the use of the method of the first aspect in detecting the migration degree of cyclosiloxane in paper packaging printed products.

[0011] The beneficial effects of this application are:

[0012] 1) The present invention proposes for the first time a method for detecting the migration degree of cyclosiloxanes in paper packaging printed materials into dry simulants, using headspace-gas chromatography / mass spectrometry and optimized conditions to detect the content of cyclosiloxanes in samples, with high sensitivity, recovery rate and precision.

[0013] 2) The present invention simultaneously adds a matrix corrector, a blank paper matrix and an internal standard to the standard solution, the paper packaging printed product sample and the dry simulant sample, thereby effectively improving the response signal, detection accuracy and repeatability of the analyte;

[0014] 3) The present invention analyzes the three-phase equilibrium theory for the detection of paper packaging printed materials for the first time, providing theoretical support for the proposed headspace-based method for detecting cyclosiloxane substances in paper packaging printed materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 Shown is the chromatogram of Comparative Example 1 of the present invention;

[0016] Among them, 1 is tetrakis(trimethylsilyl)orthosilicate (ISTD, internal standard); 2 is white cardboard + ISTD; 3 is 0.5μg / mL standard solution (including ISTD); 4 is white cardboard + 0.5μg / mL standard solution (including ISTD).

[0017] Figure 2 Shown is a chromatogram of Comparative Example 2 of the present invention that is not corrected by the internal standard;

[0018] Among them, 1 is 225g / m 2 White card paper + 0.5μg / mL standard solution (including ISTD); 2 is 38g / m 2 Mudanjiang No. 1 + 0.5μg / mL standard solution (including ISTD); 3 is 34g / mL 2 1190 white base paper + 0.5μg / mL standard solution (including ISTD).

[0019] Figure 3 Shown is the chromatogram after internal standard correction of Comparative Example 3 of the present invention;

[0020] Among them, 1 is 225g / m 2 White card paper + 0.5μg / mL standard solution (including ISTD); 2 is 38g / m 2 Mudanjiang No. 1 + 0.5μg / mL standard solution (including ISTD); 3 is 34g / mL 2 1190 white base paper + 0.5μg / mL standard solution (including ISTD).

[0021] Figure 4 Shown is the chromatogram of Comparative Example 4 of the present invention using different matrix calibrants. DETAILED DESCRIPTION

[0022] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0023] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are for describing the specific embodiments rather than for limiting the scope of protection of the present invention; in the present specification and claims, unless otherwise expressly stated herein, the singular forms "a", "an" and "the" include plural forms.

[0024] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.

[0025] The present application proposes for the first time a method for detecting the degree of migration of cyclosiloxanes in paper packaging printed materials into dry simulants, optimizes the detection conditions, and uses a headspace-gas chromatography / mass spectrometer and optimized conditions to detect the content of cyclosiloxanes in the sample to obtain the migration amount of cyclosiloxanes in paper packaging printed materials into dry simulants. By adding matrix correctors, blank paper matrix and internal standards, the response signal, detection accuracy and repeatability of the measured object are effectively improved, and the three-phase equilibrium theory during the detection of paper packaging printed materials is analyzed, providing theoretical support for the proposed headspace-based detection of cyclosiloxanes in paper packaging printed materials.

[0026] The present application first provides a method for detecting the migration degree of cyclosiloxane in paper packaging printed matter, the method comprising the following steps:

[0027] 1) Carry out migration test on the paper packaging printed matter and dry simulant to obtain the dry simulant after migration.

[0028] 2) preparing a standard working solution, preparing a paper packaging printed product sample solution with the paper packaging printed product to be tested, and preparing a dry simulant sample solution with the migrated dry simulant obtained in S1); the standard working solution, the paper packaging printed product sample solution, and the dry simulant sample solution include an internal standard.

[0029] 3) Using headspace-gas chromatography / mass spectrometry to detect the cyclosiloxane in the standard working solution, the paper packaging printed matter sample solution and the dry simulant sample solution; using the standard working curve, the content of the cyclosiloxane in the paper packaging printed matter sample solution and the dry simulant sample solution is obtained, and the migration amount and mobility are obtained.

[0030] The paper packaging printed matter refers to packaging products made of paper as a material through a printing process. Such products are widely used in the packaging of various commodities, such as food, beverages, cosmetics, medicines, electronic products, etc.

[0031] The migration degree of cyclosiloxane in the paper packaging print refers to the amount of migration of the cyclosiloxane compound (usually used as a waterproof, moisture-proof or oil-proof treatment agent) used in the packaging material into the packaging contents (such as food, beverages, etc.) under specific conditions. In the present application, the migration degree includes the migration amount and the migration rate. The migration degree of cyclosiloxane in the paper packaging print is expressed by the migration amount and the migration rate.

[0032] The dry simulant refers to a dry environment or dry material used to simulate actual contact conditions when performing a chemical migration test. In a specific embodiment of the present application, the dry simulant can be MPPO or TenaxTA.

[0033] The cyclosiloxane is a type of organic silicon compound containing epoxy functional groups. In a specific embodiment of the present application, the cyclosiloxane includes but is not limited to hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

[0034] An internal standard is a substance of known quantity and stable nature, which is added to a sample or a standard solution to improve the accuracy and repeatability of the analysis by compensating for volume changes, injection volume changes, detector response changes, and degradation or loss of sample components that may occur during sample processing and analysis. In a specific embodiment of the present application, the internal standard is tetrakis(trimethylsilyl)orthosilicate.

[0035] In a specific embodiment of the present application, the solvent of the standard working solution is triacetin and / or n-hexane.

[0036] In a specific embodiment of the present application, the solvent of the paper packaging printed matter sample solution is triacetin and / or n-hexane, which can be used as a matrix corrector to reduce the matrix effect during headspace analysis, so that the sample has the same solvent as the standard solution during analysis, thereby improving the accuracy of the sample quantitative analysis results.

[0037] In a specific embodiment of the present application, the solvent of the dry simulant sample solution is triacetin and / or n-hexane, which can be used as a matrix corrector to reduce the matrix effect during headspace analysis, so that the sample has the same solvent as the standard solution during analysis, thereby improving the accuracy of the sample quantitative analysis results.

[0038] In a specific embodiment of the present application, the solvents of the standard working solution, the paper packaging printing sample solution, and the dry simulant sample solution remain consistent.

[0039] In a specific embodiment of the present application, the standard working solution and / or the dry simulant sample solution further comprises a blank paper matrix. The paper matrix will affect the signal of the analyte, and by adding the blank paper matrix, the paper matrix can be corrected to a certain extent, and is conducive to the improvement of the analyte signal without increasing the blank signal interference.

[0040] In a specific embodiment of the present application, the blank paper substrate includes but is not limited to white card paper, coated paper, or white base paper.

[0041] In a specific embodiment of the present application, the blank paper matrix is ​​consistent with the paper of the paper packaging printed product to be tested, thereby minimizing the influence of the paper matrix on the signal of the object to be tested.

[0042] In a specific embodiment of the present application, the area of ​​the blank paper substrate can be 80 cm 2 ~180cm 2 , for example, it can be 80cm 2 ~90cm 2 , 90cm 2 ~100cm 2 , 100cm 2 ~110cm 2 , 110cm 2 ~120cm 2 , 120cm 2 ~130cm 2 , 130cm 2 ~140cm 2 , 140cm 2 ~150cm 2 , 150cm 2 ~160cm 2 , 160cm 2 ~170cm 2 , 170cm 2 ~180cm 2 .

[0043] In a specific embodiment of the present application, the blank paper substrate can be obtained by baking at 80°C to 100°C for 2h to 3h. For example, the baking temperature can be 80°C to 85°C, 85°C to 90°C, 90°C to 95°C, 95°C to 100°C, and the baking time can be 2h to 2.2h, 2.2h to 2.4h, 2.4h to 2.6h, 2.6h to 2.8h, 2.8h to 3h. By baking, moisture in the paper is removed, the structure and chemical composition of the paper are stabilized, and components that may mask or interfere with the target chemical substances are removed, thereby ensuring accuracy during the test.

[0044] In a specific embodiment of the present application, in step 1), the migration test is to place the paper packaging printed matter to be tested in contact with a dry simulant in a closed container. Through the following contact conditions, the cyclosiloxane in the paper packaging printed matter to be tested can effectively migrate to the dry simulant, thereby ensuring the accuracy of the migration test.

[0045] In a specific embodiment of the present application, the contact placement temperature can be 40℃~70℃, for example, 40℃~45℃, 45℃~50℃, 50℃~55℃, 55℃~60℃, 60℃~65℃, 65℃~70℃.

[0046] In a specific embodiment of the present application, the contact placement time can be 2h to 240h, for example, it can be 2h to 20h, 20h to 40h, 40h to 60h, 60h to 80h, 80h to 100h, 100h to 120h, 120h to 140h, 140h to 160h, 160h to 180h, 180h to 200h, 200h to 220h, 220h to 240h.

[0047] In a specific embodiment of the present application, in the migration test, the mass of the dry simulant can be 0.5g to 5g, for example, 0.5g to 1g, 1g to 1.5g, 1.5g to 2g, 2g to 2.5g, 2.5g to 3g, 3g to 3.5g, 3.5g to 4g, 4g to 4.5g, 4.5g to 5g.

[0048] In a specific embodiment of the present application, in the migration test, the ratio of the mass of the dry simulant to the area of ​​the paper packaging printed matter to be tested can be 2 to 20:1 g / dm 2 , for example, it can be 2 to 4:1 g / dm 2 , 4-6: 1g / dm 2 , 6~8:1g / dm 2 , 8~10:1g / dm 2 , 10~12:1g / dm 2 , 12~14:1g / dm2 , 14-16: 1g / dm 2 , 16-18: 1g / dm 2 , 18~20:1g / dm 2 .

[0049] In a specific embodiment of the present application, in step 2), the standard working solution is prepared as follows: accurately weigh 4 kinds of cyclosiloxane standards, 100 mg each, a 50 mL volumetric flask, and prepare a mixed standard stock solution I with a concentration of 2000 μg / mL using n-hexane as solvent; pipette 2.5 mL of the mixed standard stock solution I into a 50 mL volumetric flask, and prepare a mixed standard stock solution II with a concentration of 100 μg / mL using triacetin as solvent; pipette 5000 μL, 2000 μL, 1000 μL, 500 μL, 200 μL, 100 μL, 50 μL, and 20 μL of the mixed standard stock solution II into a 100 mL volumetric flask, and accurately add 1 mL 100μg / mL internal standard, dilute to 100mL with triacetin to obtain standard solution III with concentration range of 5μg / mL, 2μg / mL, 1μg / mL, 0.5μg / mL, 0.2μg / mL, 0.1μg / mL, 0.05μg / mL, 0.02μg / mL; add 1mL of standard solution III into 20mL headspace vials respectively, cut the blank sample matrix, roll it into a tube, immediately put it into the headspace vial, and seal it to obtain a series of standard working solutions with a concentration range of 0.02μg / mL to 5μg / mL.

[0050] In a specific embodiment of the present application, the concentration of the standard working solution can be 0.02μg / mL to 5μg / mL, for example, 0.02μg / mL to 0.05μg / mL, 0.05μg / mL to 0.1μg / mL, 0.1μg / mL to 0.2μg / mL, 0.2μg / mL to 0.5μg / mL, 0.5μg / mL to 1μg / mL, 1μg / mL to 2μg / mL, 2μg / mL to 5μg / mL.

[0051] In a specific embodiment of the present application, in the standard working solution, the concentration of the internal standard can be 0.5μg / mL to 5μg / mL, for example, 0.5μg / mL to 1μg / mL, 1μg / mL to 1.5μg / mL, 1.5μg / mL to 2μg / mL, 2μg / mL to 2.5μg / mL, 2.5μg / mL to 3μg / mL, 3μg / mL to 3.5μg / mL, 3.5μg / mL to 4μg / mL, 4μg / mL to 4.5μg / mL, 4.5μg / mL to 5μg / mL, which can maximize the accuracy and repeatability of the analysis and compensate for volume changes, injection volume changes, detector response changes, and degradation or loss of sample components that may occur during sample processing and analysis.

[0052] In a specific embodiment of the present application, in step 2), the method of preparing the paper packaging printed matter to be tested into a paper packaging printed matter sample solution is: cutting the paper packaging printed matter to be tested into samples and placing them in a container, adding a solvent containing an internal standard and sealing the container to obtain a paper packaging printed matter sample solution.

[0053] In a specific embodiment of the present application, the container is a headspace bottle.

[0054] In a specific implementation of the present application, the cut sample is rolled into a tube with the printed surface facing inward and placed in a container, which is beneficial to maintaining the integrity of the sample.

[0055] In a specific embodiment of the present application, the solvent containing the internal standard is an internal standard working solution.

[0056] In a specific embodiment of the present application, the internal standard working solution is prepared by the following method: accurately weigh 250 mg of tetrakis(trimethylsilyl)orthosilicate (ISTD), accurate to 0.1 mg, and put it into a 50 mL volumetric flask, and use n-hexane as solvent to prepare a primary internal standard stock solution with a concentration of 5000 μg / mL; take 1 mL of the primary internal standard stock solution in a 50 mL volumetric flask, and use triacetin as solvent to prepare a secondary internal standard stock solution with a concentration of 100 μg / mL; take 1 mL of the secondary internal standard stock solution in a 100 mL volumetric flask, and use triacetin as solvent to prepare an internal standard working solution with a concentration of 1 μg / mL.

[0057] In a specific embodiment of the present application, the internal standard and the solvent are added by adding a solvent containing an internal standard, ie, an internal standard working solution, so that the paper packaging printed matter to be tested is made into a paper packaging printed matter sample solution.

[0058] In a specific embodiment of the present application, in the paper packaging printed matter sample solution, the concentration of the internal standard is 0.5μg / mL to 5μg / mL; for example, it can be 0.5μg / mL to 1μg / mL, 1μg / mL to 1.5μg / mL, 1.5μg / mL to 2μg / mL, 2μg / mL to 2.5μg / mL, 2.5μg / mL to 3μg / mL, 3μg / mL to 3.5μg / mL, 3.5μg / mL to 4μg / mL, 4μg / mL to 4.5μg / mL, 4.5μg / mL to 5μg / mL, which can maximize the accuracy and repeatability of the analysis and compensate for volume changes, injection volume changes, detector response changes, and degradation or loss of sample components that may occur during sample processing and analysis.

[0059] In a specific embodiment of the present application, the paper packaging printed material to be tested is obtained by baking at 80°C to 100°C for 2h to 3h. For example, the baking temperature can be 80°C to 85°C, 85°C to 90°C, 90°C to 95°C, 95°C to 100°C, and the baking time can be 2h to 2.2h, 2.2h to 2.4h, 2.4h to 2.6h, 2.6h to 2.8h, 2.8h to 3h. By baking, moisture in the paper is removed, the structure and chemical composition of the paper are stabilized, and components that may mask or interfere with the target chemical substances are removed, thereby ensuring accuracy during the test.

[0060] In a specific embodiment of the present application, the area of ​​the sample can be 80 cm 2 ~180cm 2 , for example, it can be 80cm 2 ~90cm 2 , 90cm 2 ~100cm 2 , 100cm 2 ~110cm 2 , 110cm 2 ~120cm 2 , 120cm 2 ~130cm 2 , 130cm 2 ~140cm 2 , 140cm 2 ~150cm 2 , 150cm 2 ~160cm 2 , 160cm 2 ~170cm 2 , 170cm 2 ~180cm 2 to ensure the accuracy of detection.

[0061] In a specific embodiment of the present application, the method for preparing a dry simulant sample solution from the dry simulant after the migration test obtained in S1) is: transferring the dry simulant after the migration test into a container, adding a solvent containing an internal standard for extraction, performing solid-liquid separation, and obtaining a dry simulant sample solution after purification.

[0062] In a specific embodiment of the present application, the solvent containing the internal standard is an internal standard working solution.

[0063] In a specific embodiment of the present application, the internal standard working solution is prepared by the following method: accurately weigh 250 mg of tetrakis(trimethylsilyl)orthosilicate (ISTD), accurate to 0.1 mg, a 50 mL volumetric flask, and prepare a primary internal standard stock solution with a concentration of 5000 μg / mL using n-hexane as solvent; take 1 mL of the primary internal standard stock solution in a 50 mL volumetric flask, and prepare a secondary internal standard stock solution with a concentration of 100 μg / mL using triacetin as solvent; take 1 mL of the secondary internal standard stock solution in a 100 mL volumetric flask, and prepare an internal standard working solution with a concentration of 1 μg / mL using triacetin as solvent. In a specific embodiment of the present application, the container is a headspace bottle.

[0064] In a specific embodiment of the present application, an internal standard and a solvent are added by adding a solvent containing an internal standard, i.e., an internal standard working solution, and the cyclosiloxane in the dry simulant is extracted by the internal standard working solution, and the solid-liquid separation and purification are performed, thereby preparing a dry simulant sample solution from the dry simulant after the migration test.

[0065] In a specific embodiment of the present application, in the dry simulant sample solution, the concentration of the internal standard can be 0.5μg / mL to 5μg / mL; for example, it can be 0.5μg / mL to 1μg / mL, 1μg / mL to 1.5μg / mL, 1.5μg / mL to 2μg / mL, 2μg / mL to 2.5μg / mL, 2.5μg / mL to 3μg / mL, 3μg / mL to 3.5μg / mL, 3.5μg / mL to 4μg / mL, 4μg / mL to 4.5μg / mL, 4.5μg / mL to 5μg / mL, which can maximize the accuracy and repeatability of the analysis and compensate for volume changes, injection volume changes, detector response changes, and degradation or loss of sample components that may occur during sample processing and analysis.

[0066] In a specific embodiment of the present application, the extraction time can be 5 min to 50 min, for example, 5 min to 10 min, 10 min to 15 min, 15 min to 20 min, 20 min to 25 min, 25 min to 30 min, 30 min to 35 min, 35 min to 40 min, 40 min to 45 min, 45 min to 50 min.

[0067] In a specific embodiment of the present application, the rotation speed during extraction can be 500r / min~1500r / min, for example, it can be 500r / min~600r / min, 600r / min~700r / min, 700r / min~800r / min, 800r / min~900r / min, 900r / min~1000r / min, 1000r / min~1100r / min, 1100r / min~1200r / min, 1200r / min~1300r / min, 1300r / min~1400r / min, 1400r / min~1500r / min.

[0068] In one embodiment of the present application, the extraction may be performed using a vortex oscillator, which, under the above conditions, is conducive to maximally extracting the cyclosiloxane in the dry simulant sample solution.

[0069] In a specific embodiment of the present application, the solid-liquid separation uses a centrifuge, which is conducive to complete separation of the solid phase and the liquid phase after extraction under the following conditions.

[0070] In a specific embodiment of the present application, the centrifugation time can be 5 min to 10 min, for example, 5 min to 6 min, 6 min to 7 min, 7 min to 8 min, 8 min to 9 min, 9 min to 10 min.

[0071] In a specific embodiment of the present application, the centrifugal rotation speed can be 5000r / min~10000r / min, for example, it can be 5000r / min~6000r / min, 6000r / min~7000r / min, 7000r / min~8000r / min, 8000r / min~9000r / min, 9000r / min~10000r / min.

[0072] In a specific embodiment of the present application, the purification adopts base phase membrane filtration.

[0073] In a specific embodiment of the present application, the pore size of the base phase filter membrane is 0.22 μm or 0.45 μm.

[0074] In a specific embodiment of the present application, the standard curve uses the ratio of the quantitative ion peak area of ​​cyclosiloxane to the quantitative ion peak area of ​​the internal standard as the ordinate, and uses the content of cyclosiloxane as the abscissa.

[0075] In a specific embodiment of the present application, the method for obtaining the content of cyclosiloxane in a paper packaging printed matter sample solution through a standard working curve is as follows: the content of cyclosiloxane in the paper packaging printed matter sample solution is calculated using the standard working curve and the ratio of the quantitative ion peak area of ​​cyclosiloxane corresponding to the paper packaging printed matter sample solution to the quantitative ion peak area of ​​the internal standard.

[0076] In a specific embodiment of the present application, the method for obtaining the content of cyclosiloxane in the dry simulant sample solution is: the content of cyclosiloxane in the dry simulant sample solution is calculated using the standard working curve and the ratio of the quantitative ion peak area of ​​cyclosiloxane corresponding to the dry simulant sample solution to the quantitative ion peak area of ​​the internal standard.

[0077] In a specific embodiment of the present application, the content of cyclosiloxane in the dry simulant sample solution is the migration amount.

[0078] In a specific embodiment of the present application, the mobility is calculated according to the following formula: mobility = content of cyclosiloxane in the dry simulant sample solution / content of cyclosiloxane in the paper packaging printed matter sample solution.

[0079] In the present application, a three-phase equilibrium of the paper packaging printed matter to be tested, triacetin and a gas sample exists in the paper packaging printed matter sample solution: by measuring the gas phase concentration of the volatile component in the headspace, the original concentration C0 of the volatile component in the paper packaging printed matter to be tested can be determined.

[0080] At a certain temperature, when the volatile components reach equilibrium in the gas, liquid and solid phases, the volatile components also reach equilibrium in the solid-gas, solid-liquid and liquid-gas phases respectively. The ratio of the concentrations of the volatile components in the two phases is defined as the distribution constant.

[0081]

[0082] In formula (1), K1 is the solid-gas partition constant, C sa is the equilibrium concentration of the volatile components in the paper that is in contact with the gas phase, C a is the equilibrium concentration of the component in the gas phase, and β1 is the gas-to-solid ratio.

[0083]

[0084] In formula (2), K2 is the solid-liquid partition constant, C sl is the equilibrium concentration of the volatile components in the paper that is in contact with the liquid phase, Cl is the equilibrium concentration of the component in the liquid phase, and β2 is the liquid-to-solid ratio.

[0085]

[0086] In formula (3), K3 is the liquid-gas distribution constant, C l is the equilibrium concentration of the component in the liquid phase, C a is the equilibrium concentration of the component in the gas phase, and β3 is the gas-liquid phase ratio.

[0087] In a closed system, the mass balance equation of the three-phase system can be expressed as:

[0088] C0V p =C sa V sa +C sl V sl +C a V a +C l V l (4)

[0089] In formula (4), C0 is the original concentration of volatile components in paper, V p is the volume of the paper.

[0090] Substituting equations (1), (2) and (3) into equation (4), we obtain:

[0091] C0V p =K1C a V sa +K2K3C a V sl +C a V a +K3C a V l

[0092] =C a (K1V sa +K2K3V sl +V a +K3V l )

[0093] =C a (K1V sa +K2K3V sa β1 / (β2β3)+β1V sa +K3β1V sa / β3)

[0094] =C a V sa (K1+K2K3β1 / (β2β3)+β1+K3β1 / β3) (5)

[0095] According to formula (5), we can get:

[0096]

[0097] V p is the volume of the paper, then:

[0098] V p =V sa +V sl (7)

[0099] According to equations (1), (2), (3), and (7), we can obtain:

[0100]

[0101] Substituting (8) into (6) we get:

[0102]

[0103] Under certain conditions, for a given equilibrium system, according to the laws of thermodynamics, K1, K2, K3, β1, β2, β3 are constants, then:

[0104] C a =C0K′, where K′=(β1+β2β3) / (K1β2β3+K2K3β1+K3β1β2+β1β2β3) (10)

[0105] According to formula (10), it can be concluded that under equilibrium conditions, the content of volatile components in the gas phase is proportional to the content of the volatile components in the original printed matter. Therefore, as long as the gas phase concentration of the volatile components in the headspace at equilibrium is determined, the original concentration C0 of the volatile components in the paper packaging printed matter to be tested can be determined.

[0106] In a specific embodiment of the present application, an Agilent 7697A-8890B-5977B headspace-gas chromatography / mass spectrometer (HS-GC / MS) is used. Through the headspace, gas chromatography and mass spectrometry conditions of the present application, various cyclosiloxanes can be effectively separated, thereby improving the response signal of the detected object, the detection accuracy and repeatability.

[0107] Specifically, under the headspace conditions, the equilibrium temperature can be 80°C to 100°C, for example, 80°C to 82°C, 82°C to 84°C, 84°C to 86°C, 86°C to 88°C, 88°C to 90°C, 90°C to 92°C, 92°C to 94°C, 94°C to 96°C, 96°C to 98°C, 98°C to 100°C.

[0108] Specifically, under the headspace conditions, the equilibrium time can be 20 min to 40 min, for example, 20 min to 22 min, 22 min to 24 min, 24 min to 26 min, 26 min to 28 min, 28 min to 30 min, 30 min to 32 min, 32 min to 34 min, 34 min to 36 min, 36 min to 38 min, 38 min to 40 min.

[0109] Specifically, under the head space conditions, the quantitative loop temperature can be 180°C to 210°C, for example, it can be 180°C to 182°C, 182°C to 184°C, 184°C to 186°C, 186°C to 188°C, 188°C to 190°C, 190°C to 192°C, 192°C to 194°C, 194°C to 196°C, 196°C to 198°C, 198°C to 200°C, 200°C to 202°C, 202°C to 204°C, 204°C to 206°C, 206°C to 208°C, 208°C to 210°C.

[0110] Specifically, under the head space conditions, the transmission line temperature can be 190°C to 220°C; for example, it can be 190°C to 192°C, 192°C to 194°C, 194°C to 196°C, 196°C to 198°C, 198°C to 200°C, 200°C to 202°C, 202°C to 204°C, 204°C to 206°C, 206°C to 208°C, 208°C to 210°C, 210°C to 212°C, 212°C to 214°C, 214°C to 216°C, 216°C to 218°C, 218°C to 220°C.

[0111] Specifically, in the gas chromatography conditions, the chromatographic column may be a VOC chromatographic column with a length of 60 m× an inner diameter of 0.32 mm× a film thickness of 1.8 μm.

[0112] Specifically, under the conditions of gas chromatography, the injection port temperature can be 200℃~250℃, for example, it can be 200℃~205℃, 205℃~210℃, 210℃~215℃, 215℃~220℃, 220℃~225℃, 225℃~230℃, 230℃~235℃, 235℃~240℃, 240℃~245℃, 245℃~250℃.

[0113] Specifically, in the gas chromatography condition, the carrier gas is helium, and the purity of the helium is ≥ 99.999%.

[0114] Specifically, under the conditions of gas chromatography, the flow rate can be 1mL / min to 3mL / min, for example, it can be 1mL / min to 1.2mL / min, 1.2mL / min to 1.4mL / min, 1.4mL / min to 1.6mL / min, 1.6mL / min to 1.8mL / min, 1.8mL / min to 2mL / min, 2mL / min to 2.2mL / min, 2.2mL / min to 2.4mL / min, 2.4mL / min to 2.6mL / min, 2.6mL / min to 2.8mL / min, 2.8mL / min to 3mL / min.

[0115] Specifically, under the conditions of gas chromatography, the split ratio can be (10-15):1, for example, (10-11):1, (11-12):1, (12-13):1, (13-14):1, (14-15):1.

[0116] Specifically, in the conditions of gas chromatography, the temperature rising program can be isothermal or gradient temperature rising, and the temperature rising program can be an initial temperature of 35°C to 45°C, maintained for 1min to 3min, and then heated to 190°C to 210°C at a rate of 2°C / min to 5°C / min, and maintained for 8min to 12min; for example, the initial temperature can be 35°C to 36°C, 36°C to 37°C, 37°C to 38°C, 38°C to 39°C, 39°C to 40°C, 40°C to 41°C, 41°C to 42°C, 42 ℃~43℃, 43℃~44℃, 44℃~45℃; the holding time can be 1min~2min, 2min~3min; the rate can be 2℃ / min~3℃ / min, 3℃ / min~4℃ / min, 4℃ / min~5℃ / min, the heating temperature can be 190℃~200℃, 200℃~210℃, and the holding time can be 8min~9min, 9min~10min, 10min~11min, 11min~12min.

[0117] Specifically, under the conditions of mass spectrometry, the transmission line temperature can be 230℃~280℃, for example, 230℃~235℃, 235℃~240℃, 240℃~245℃, 245℃~250℃, 250℃~255℃, 255℃~260℃, 260℃~265℃, 265℃~270℃, 270℃~275℃, 275℃~280℃.

[0118] Specifically, under the conditions of mass spectrometry, the ion source temperature can be 210℃~250℃, for example, 210℃~215℃, 215℃~220℃, 220℃~225℃, 225℃~230℃, 230℃~235℃, 235℃~240℃, 240℃~245℃, 245℃~250℃.

[0119] Specifically, under the conditions of mass spectrometry, the quadrupole temperature can be 130°C to 170°C, for example, 130°C to 135°C, 135°C to 140°C, 140°C to 145°C, 145°C to 150°C, 150°C to 155°C, 155°C to 160°C, 160°C to 165°C, 165°C to 170°C.

[0120] Specifically, in the mass spectrometry conditions, the solvent delay may be 1 min to 5 min, for example, 1 min to 2 min, 2 min to 3 min, 3 min to 4 min, 4 min to 5 min.

[0121] Specifically, in the mass spectrometry conditions, the data acquisition mode is ion monitoring.

[0122] The present application also provides the use of the above-mentioned method for detecting the migration degree of cyclosiloxane in paper packaging printed products in detecting the migration degree of cyclosiloxane in paper packaging printed products.

[0123] In a specific embodiment of the present application, the use is specifically the degree of migration of cyclosiloxane of paper packaging printed matter to a dry simulant, and the degree of migration includes a migration amount and a migration rate.

[0124] The present application is further described below by way of examples, but the scope of the present application is not limited thereby. Unless otherwise stated, the experimental methods, detection methods, and preparation methods disclosed in the present invention all adopt conventional analytical chemistry and related art conventional techniques in the art. These techniques have been well described in the existing literature. Unless otherwise specified, the instruments, materials, reagents, etc. used in the examples of the present application can be obtained by conventional means.

[0125] The examples in this application all use Agilent 7697A-8890B-5977B headspace-gas chromatograph / mass spectrometer (HS-GC / MS)

[0126] The conditions for headspace and gas chromatography were:

[0127] Equilibrium temperature 90°C; equilibrium time 30 min; quantitative loop temperature 200°C; transfer line temperature 210°C; GC cycle time 60 min; chromatographic column Supelco VOC special chromatographic column (60m×0.32mm×1.8μm); injection port temperature 220°C; carrier gas is helium (purity ≥99.999%), constant flow rate is 2mL / min; split ratio 10:1; programmed temperature rise: initial temperature is 40°C, maintained for 2 min, then heated to 200°C at a rate of 4°C / min, maintained for 10 min.

[0128] The conditions for mass spectrometry were as follows:

[0129] The ion source temperature was 230°C, and the quadrupole temperature was 150°C; the determination method was selected ion monitoring; the target analytes and internal standard information are shown in Table 1.

[0130] Cyclosiloxane standards and reagents: Hexamethylcyclotrisiloxane (97.0%), SIGMA-ALDRICH; Octamethylcyclotetrasiloxane (analytical grade), SIGMA-ALDRICH; Decamethylcyclopentasiloxane (99.0%), Shanghai Anpu Experimental Technology Co., Ltd.; Dodecamethylcyclohexasiloxane (98.0%), Tokyo Chemical Industry Co., Ltd.; Tetrakis(trimethylsilyl)orthosilicate (99.7%), CATO Research Chmicals Inc; Glyceryl triacetate (99.0%), Shanghai Anpu Experimental Technology Co., Ltd.

[0131] Table 1 Target analytes and internal standard information

[0132]

[0133]

[0134] Example 1 Establishing a standard working curve

[0135] 1. Preparation of internal standard solution

[0136] 1) Primary internal standard stock solution

[0137] Accurately weigh 250 mg of tetrakis(trimethylsilyl)orthosilicate (ISTD) to an accuracy of 0.1 mg, put it into a 50 mL volumetric flask, use n-hexane as solvent to prepare an internal standard solution with a concentration of 5000 μg / mL, and store it at 4°C in the dark.

[0138] 2) Secondary internal standard stock solution

[0139] Take 1 mL of the primary internal standard stock solution in a 50 mL volumetric flask and prepare a secondary internal standard stock solution with a concentration of 100 μg / mL using triacetin as solvent.

[0140] 3) Internal standard working solution

[0141] Take 1 mL of the secondary internal standard stock solution in a 100 mL volumetric flask and prepare an internal standard working solution with a concentration of 1 μg / mL using triacetin as solvent. In subsequent experiments, the internal standard and solvent were added by adding the internal standard working solution.

[0142] 2. Preparation of standard solution

[0143] 1) Primary standard stock solution

[0144] Weigh 100 mg of each of the four cyclosiloxane standards into a 50 mL volumetric flask, prepare a mixed standard stock solution with a concentration of 2000 μg / mL using n-hexane as solvent, and store at 4°C in the dark.

[0145] 2) Secondary standard stock solution

[0146] Pipette 2.5 mL of the primary standard stock solution into a 50 mL volumetric flask, prepare a secondary standard stock solution with a concentration of 100 μg / mL using triacetin as solvent, and store at 4°C in the dark.

[0147] 3) Standard solution

[0148] Prepare a mixed standard solution of appropriate concentration as needed. Prepare as follows: pipette 5000μL, 2000μL, 1000μL, 500μL, 200μL, 100μL, 50μL, and 20μL of the secondary standard stock solution into a 100mL volumetric flask, accurately add 1mL of the secondary internal standard stock solution, and dilute to 100mL with triacetin to obtain a series of standard solutions. The concentrations of the prepared series of standard solutions are 5μg / mL, 2μg / mL, 1μg / mL, 0.5μg / mL, 0.2μg / mL, 0.1μg / mL, 0.05μg / mL, and 0.02μg / mL.

[0149] Take the outer packaging paper (225g / m 2 White cardboard), lining paper (38g / m 2 Mudanjiang No. 1) was used as a blank paper substrate and treated at 90 °C for 2 h.

[0150] Cut the corresponding paper base paper (outer packaging paper base paper 121cm 2 、Inner lining paper 170cm 2), roll the paper sample into a tube and immediately put it into the headspace bottle; add 1mL of standard working solution of different concentrations respectively, seal it and perform HS-GC / MS analysis. The ordinate is the ratio of the peak area of ​​the quantitative ion of each analyte to the peak area of ​​the quantitative ion of the internal standard, and the abscissa is the concentration of each analyte. The standard working curve is drawn. The results are shown in Table 2. It can be seen from the table that the linear correlation coefficient of the working curve is R 2 All of them are greater than 0.998, indicating a good linear relationship.

[0151] Table 2 Linear range and correlation coefficient of target analytes

[0152]

[0153] Example 2 Recovery and Precision Test

[0154] 1) Test on the recovery rate of cyclosiloxane substances in paper packaging and printed materials

[0155] The outer packaging paper and the inner lining paper were taken as sample matrices, and three standard solutions of low, medium and high levels were added to each matrix. Three samples were measured at each level to determine the content of four cyclosiloxane substances. The detection limit, quantitative limit, recovery rate and precision of the method were calculated. The results are shown in Table 3 and Table 4. It can be seen from the table that when the outer packaging paper is used as the matrix, the detection limit of the method is 0.0004 mg / m 2 -0.0006mg / m 2 The recovery rate was 87.0%-104.2%, and the precision was 1.3%-6.0%. When the liner paper was used as the matrix, the detection limit of the method was 0.0002mg / m 2 -0.0014mg / m 2 The recovery rate was 91.7%-100.2%, and the precision was 0.5%-7.7%. The results showed that the method had high sensitivity, good recovery rate and precision.

[0156] Table 3: Standardization of outer packaging paper

[0157]

[0158] Table 4: Standard addition of liner paper

[0159]

[0160] 2) Recovery test of cyclosiloxane substances in dry simulants

[0161] Weigh 1 g of MPPO simulant in a centrifuge tube, add three levels of standard stock solutions of low, medium and high levels respectively, and three samples for each level. After the solution is completely adsorbed by MPPO, add 10 mL of triacetin (containing ISTD 1 μg / mL), vortex oscillate at a rate of 1500 r / min for 30 min on a vortex oscillator, and then centrifuge at 8000 r / min for 5 min; take 5 mL of supernatant and filter through a 0.22 μm organic phase filter membrane for GCMS analysis to determine the contents of four cyclosiloxane substances, and calculate the detection limit, quantification limit, recovery rate and precision of the method. The results are shown in Table 5.

[0162] As can be seen from the table, the detection limit is 0.04mg / kg-0.07mg / kg, the quantification limit is 0.12mg / kg-0.25mg / kg, the recovery rate is 86.9%-109.3%, and the precision is 1.5%-7.9%. The results show that the method has high sensitivity and good recovery rate and precision.

[0163] Table 5 Linear range and correlation coefficient of target analytes

[0164]

[0165] Example 3 Extraction and detection of typical paper packaging printed matter

[0166] Take paper packaging printed materials or paper samples. For outer packaging paper samples, the cutting area is 121cm 2 For the inner liner paper sample, the cutting area is 170cm 2 The sample should include the main packaging surface. Roll the cut sample with the printed surface facing inward into a tube, immediately put it into a headspace bottle, add 1mL of internal standard working solution, seal it and perform HS-GC / MS analysis. There are 9 samples of outer packaging paper, namely sample 1 to sample 9; there are 10 samples of lining paper, namely sample 10 to sample 19.

[0167] The results are shown in Table 6. It can be seen from the table that the overall detection situation is: outer packaging paper > inner lining paper. Among them, the detection value of sample No. 9 in the outer packaging paper is higher, with D6 reaching 0.3096 mg / m 2 ; The detection value of sample No. 12 in the liner paper is slightly higher, D6 reaches 0.0215mg / m 2 .

[0168] Table 6 Test results of typical outer packaging paper and inner lining paper

[0169]

[0170]

[0171] Example 4: Extraction of simulants and detection of migration

[0172] A migration experiment was conducted at 40°C for 10 days using modified polyphenylene ether (MPPO) as a migration simulant. 2 Circular (diameter 5.64cm) sample. Weigh 1g±0.001g MPPO in a glass petri dish, spread evenly, and place 0.25dm 2 Lay the inner liner paper (aluminum foil facing up) flat on top of the MPPO, and then place a 0.25dm 2 The outer packaging paper (printed side facing upward) is placed on the surface of the inner lining paper, and the glass culture dish is covered and sealed, and placed in a constant temperature box. The test temperature is set to 40°C. After the contact time is 240 hours, the glass culture dish is taken out from the constant temperature box to obtain the MPPO test sample containing the migration substance to be tested.

[0173] Transfer the MPPO in the culture dish to a centrifuge tube, weigh the mass, add 10 mL of the internal standard working solution (1 μg / mL), vortex and oscillate at a rate of 1500 r / min for 30 min on a vortex oscillator, and then centrifuge at 8000 r / min for 5 min; take 5 mL of the supernatant and filter it through a 0.22 μm organic phase filter membrane; take 1 mL of the filtrate after filtration and 121 cm 2 Blank paper matrix was analyzed by GCMS in headspace vials.

[0174] The common migration amount and migration rate of cyclosiloxane substances in the outer packaging paper and the inner lining paper were tested, and the results are shown in Table 7. From the data in the table, it can be seen that the main common migrant is D6, and the migration amounts are 0.1720mg / kg±0.0017mg / kg, 0.1254mg / kg±0.0092mg / kg and 0.4210mg / kg±0.0042mg / kg, respectively, and the corresponding migration rates are 64.10%, 67.22% and 54.39%, respectively.

[0175] Table 7 Test results of the common migration of outer packaging paper and inner lining paper

[0176]

[0177] Comparative Example 1 Effect of Blank Paper Matrix

[0178] In order to investigate the influence of paper matrix on the sample analysis signal, blank samples and spiked samples (spiked concentration was 0.5 μg / mL) were tested using white cardboard as the matrix. The results are shown in Figure 1 As can be seen from the figure, after adding the white cardboard substrate, the responses of the four target substances in the blank sample did not change significantly compared with those without the addition of the white cardboard substrate, while in the spiked sample, the responses of the four target substances were significantly enhanced compared with those without the addition of the white cardboard substrate, indicating that the addition of the white cardboard substrate is beneficial to the improvement of the signal of the measured object and does not increase the interference of the blank signal.

[0179] Comparative Example 2 Effect of Paper Matrix

[0180] Furthermore, this example uses spiked positive samples to investigate the signal responses of different paper matrix samples. Figure 2 It can be seen that the three samples are significantly different, indicating that the paper matrix has a greater impact.

[0181] Effect of internal standard in comparative example 3

[0182] The spectrum in comparative example 2 was corrected by internal standard, and the results are shown in Figure 3 As can be seen from the figure, after internal standard correction, it can be seen that the response differences of the three are small, indicating that the internal standard can effectively correct the fluctuation of the signal caused by different paper matrices. In order to further reduce the influence of the sample matrix, when establishing the standard curve, the experiment tried to select a paper matrix that was closer to the sample matrix (baked at 90℃ for 2h, cut to the same area as the sample) and add it to the headspace bottle, and then add a series of standard working solutions for analysis.

[0183] Effect of Matrix Corrector in Comparative Example 4

[0184] In headspace analysis, matrix calibrants are often added to reduce matrix effects so that the sample has the same solvent as the standard solution during analysis, thereby improving the accuracy of the sample quantitative analysis results. In this experiment, n-hexane and triacetin were selected as matrix calibrants, and the repeatability of the test after matrix correction was investigated by the relative standard deviation of the peak area of ​​the analyte. The results are shown in Figure 4 As can be seen from the figure, when triacetin is used as the matrix calibrant, the peak area reproducibility of the four target substances is good, ranging from 4.0% to 5.5%; when n-hexane is used as the matrix calibrant, the peak area reproducibility is poor, ranging from 14.7% to 27.7%. Therefore, triacetin is selected as the matrix calibrant in the experiment, that is, triacetin is selected as the solvent.

[0185] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.

Claims

1. A method for detecting the migration degree of cyclosiloxane in paper packaging printed matter, characterized in that: The method comprises the following steps: 1) Conducting a migration test on the paper packaging printed matter and the dry simulant to obtain the dry simulant after migration; 2) preparing a standard working solution, preparing a paper packaging printed product sample solution with the paper packaging printed product to be tested, and preparing a dry simulant sample solution with the migrated dry simulant; the standard working solution, the paper packaging printed product sample solution, and the dry simulant sample solution include an internal standard; 3) Using headspace-gas chromatography / mass spectrometry to detect the cyclosiloxane in the standard working solution, the paper packaging printed matter sample solution and the dry simulant sample solution; using the standard working curve, the content of the cyclosiloxane in the paper packaging printed matter sample solution and the dry simulant sample solution is obtained, and the migration amount and mobility are obtained.

2. The method according to claim 1, characterized in that The cyclosiloxane is selected from any one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.

3. The method according to claim 1, characterized in that The headspace conditions in the headspace-gas chromatograph / mass spectrometer are: equilibrium temperature of 80°C to 100°C; equilibrium time of 20min to 40min; quantitative loop temperature of 180°C to 210°C; and transmission line temperature of 190°C to 220°C. And / or, the gas chromatography conditions in the headspace-gas chromatography / mass spectrometer are: the chromatographic column is a VOC chromatographic column; the injection port temperature is 200°C to 250°C; the carrier gas is helium, and the helium purity is ≥99.999%; the flow rate is 1mL / min to 3mL / min; the split ratio is (10 to 15): 1; the heating program is a gradient heating program; preferably, the heating program is an initial temperature of 35°C to 45°C, maintained for 1min to 3min, and then heated to 190°C to 210°C at a rate of 2°C / min to 5°C / min, and maintained for 8min to 12min.

4. The method according to claim 1, characterized in that: The method may further include any one or more of the following features: a) the dry simulant is MPPO; b) the internal standard substance is tetrakis(trimethylsilyl)orthosilicate; c) The solvents of the standard working solution, paper packaging printed matter sample solution and dry simulant sample solution are triacetin and / or n-hexane.

5. The method according to claim 4, characterized in that The method may further include any one or more of the following features: b1) In the standard working solution, the concentration of the internal standard is 0.5 μg / mL to 5 μg / mL; b2) in the paper packaging printed matter sample solution, the concentration of the internal standard is 0.5 μg / mL to 5 μg / mL; b3) In the dry simulant sample solution, the concentration of the internal standard is 0.5 μg / mL to 5 μg / mL.

6. The method according to claim 1, characterized in that The standard working solution and / or dry simulant sample solution further comprises a blank paper matrix. Preferably, the blank paper matrix comprises white cardboard, coated paper, or white base paper; more preferably, the blank paper matrix is ​​consistent with the paper of the paper packaging printed product to be tested.

7. The method according to claim 6, characterized in that The area of ​​the blank paper substrate is 80 cm 2 ~180cm 2 ; and / or, the blank paper substrate is obtained by baking at 80°C to 100°C for 2h to 3h.

8. The method according to claim 1, characterized in that The method may further include any one or more of the following: 11) In step 1), the migration test is performed by placing the paper packaging printed matter to be tested in contact with a dry simulant in a sealed container; 21) In step 2), the concentration of the standard working solution is 0.02 μg / mL to 5 μg / mL; 22) In step 2), the method of preparing the paper packaging printed matter to be tested into a paper packaging printed matter sample solution is: cutting the paper packaging printed matter to be tested into samples and placing them in a container, adding a solvent containing an internal standard and sealing the container to obtain a paper packaging printed matter sample solution; 23) In step 2), the method of preparing the dry simulant sample solution from the migrated dry simulant obtained in S1) is as follows: transferring the simulant material obtained from the migration test into a container, adding a solvent containing an internal standard to extract, separating the solid from the liquid, and obtaining the simulant solution to be tested after purification; 31) In step 3), the standard curve has the ratio of the quantitative ion peak area of ​​cyclosiloxane to the quantitative ion peak area of ​​the internal standard as the ordinate and the content of cyclosiloxane as the abscissa; 32) In step 3), the method for obtaining the content of cyclosiloxane in the paper packaging printed matter sample solution by using the standard working curve is: using the standard working curve and the ratio of the quantitative ion peak area of ​​cyclosiloxane corresponding to the paper packaging printed matter sample solution to the quantitative ion peak area of ​​the internal standard to calculate the content of cyclosiloxane in the paper packaging printed matter sample solution; 33) In step 3), the method for obtaining the content of cyclosiloxane in the dry simulant sample solution through the standard working curve is: using the standard working curve and the ratio of the quantitative ion peak area of ​​cyclosiloxane corresponding to the dry simulant sample solution to the quantitative ion peak area of ​​the internal standard to calculate the content of cyclosiloxane in the dry simulant sample solution; 34) In step 3), the content of cyclosiloxane in the dry simulant sample solution is the migration amount, and the mobility is calculated according to the following formula: mobility = content of cyclosiloxane in the dry simulant sample solution / content of cyclosiloxane in the paper packaging printed matter sample solution.

9. The method according to claim 8, characterized in that The method may further include one or more of the following features: 111) In 11), the contacting temperature is 40°C to 70°C; 112) In 11), the contacting time is 2 hours to 240 hours; 113) In 11), the mass of the dry simulant is 0.5 g to 5 g; 114) In 11), the ratio of the mass of the dry simulant to the area of ​​the paper packaging printed matter to be tested is 2 to 20:1 g / dm 2 ; 221) In 22), the paper packaging printed product to be tested is obtained by baking at 80°C to 100°C for 2h to 3h; 222) In 22), the area of ​​the sample is 80 cm 2 ~180cm 2 ; 231) In 23), the extraction time is 5 min to 50 min, and the rotation speed during extraction is 500 r / min to 1500 r / min; 232) In 23), the solid-liquid separation is performed by centrifugation. Preferably, the centrifugation time is 5 min to 10 min, and the centrifugation speed is 5000 r / min to 10000 r / min; 233) In 23), the purification is carried out by membrane filtration; preferably, the pore size of the membrane is 0.22 μm or 0.45 μm.

10. The method according to claim 1, characterized in that The mass spectrometry conditions in the headspace-gas chromatography / mass spectrometer are: the transmission line temperature is 230°C to 280°C; the ion source temperature is 210°C to 250°C; the quadrupole temperature is 130°C to 170°C; the solvent delay is 1min to 5min; and the data acquisition mode is ion monitoring.

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