Method for detecting migration volume of non-phthalate plasticizer in paper packaging product

Abstract

The invention belongs to the technical field of analysis and detection, and relates to a method for detecting the migration volume of non-phthalate plasticizers in paper packaging products. The invention provides a method for detecting the migration volume of a non-phthalate plasticizer in a paper packaging product, which comprises the following steps: carrying out migration test on a paper packaging product to be detected and a dry simulant to obtain a migrated dry simulant; preparing a standard working solution; preparing a to-be-detected simulant solution from the obtained migrated dry simulant; the standard working solution and the to-be-detected simulant solution comprise an internal standard substance; and detecting the standard working solution and the to-be-detected simulant solution by adopting a gas chromatography mass spectrometer, and calculating the content of the non-phthalate plasticizer in the to-be-detected simulant solution according to the standard curve. The method is high in analysis speed, high in precision and good in accuracy, and typical non-phthalate plasticizers can be detected at the same time.

Description

Technical Field

[0001] The invention belongs to the technical field of analysis and detection, and relates to a method for detecting the migration amount of non-phthalate plasticizers in paper packaging products. Background Art

[0002] Plasticizers are commonly used in packaging materials, medical, decoration, ink, personal care products and other products. According to the chemical structure, they can be divided into phthalates, phosphates, benzoates, citrates, etc. Phthalates are the most widely used type. However, since phthalate plasticizers can interfere with the secretion of normal human hormones and cause harm to the human body, the research on non-phthalate plasticizers has received great attention. Although non-phthalate plasticizers are less toxic than phthalate plasticizers, their compliance risks and harm to the human body are gradually becoming apparent as the scope and amount of use increase.

[0003] At present, there are few reports on the detection technology of non-phthalate plasticizers. They are mainly extracted by ultrasound assistance and solvent extraction, purified by filter membrane, and finally analyzed by gas chromatography-mass spectrometry. The research on the migration of related substances is almost blank. However, the migration index plays an important role and has reference value for the risk assessment of chemical substances. In view of the above analysis, the current research on non-phthalate plasticizers has the following shortcomings:

[0004] 1) There is no report on the detection method of non-phthalate esters migration into dry simulants, and the research on migration of dry simulants is blank.

[0005] 2) Different types of non-phthalate plasticizers have quite different chemical properties. There are some methods for analyzing the same type of non-phthalate plasticizers in the prior art, but there are few studies on detection methods suitable for multiple types of typical non-phthalate plasticizers.

[0006] 3) During the detection of plasticizers, when the concentration range is wide, the standard curve is prone to quadratic curve phenomenon, and gas chromatography-mass spectrometry technology usually uses linear fitting to process standard curve information for subsequent experimental data analysis. Due to the large differences in the types and contents of non-o-phthalate plasticizers used in the actual production process, it is difficult to establish a linear standard curve to meet the detection of non-o-phthalate substances with large concentration ranges in products. Summary of the invention

[0007] Based on the defects of the above-mentioned prior art, this application proposes for the first time a method for detecting the migration of non-phthalate plasticizers in paper packaging products into dry simulants. By analyzing the characteristics of paper packaging materials, optimizing the pretreatment method, and screening suitable internal standards, a method is used to accurately detect multiple types of typical non-phthalate plasticizers. By optimizing the size of the split ratio and selecting an ion lens with a suitable aperture for the experiment, the linearity problem of the standard curve of non-phthalate plasticizers in a wide concentration range is solved.

[0008] The first aspect of the present application provides a method for detecting the migration amount of non-phthalate plasticizers in paper packaging products, characterized in that the detection method comprises the following steps:

[0009] S1) performing a migration test on the paper packaging product to be tested and the dry simulant to obtain the dry simulant after migration;

[0010] S2) preparing a standard working solution, and preparing the migrated dry simulant obtained in S1) into a simulant solution to be tested; the standard working solution and the simulant solution to be tested include an internal standard;

[0011] S3) using a gas chromatography-mass spectrometer to detect the standard working solution and the simulant solution to be tested, and calculating the non-phthalate plasticizer content in the simulant solution to be tested according to the standard curve.

[0012] The non-phthalate plasticizer is selected from any one or more of diethyl adipate, diisobutyl adipate, dibutyl adipate, bis(2-butoxyethyl) adipate, diisooctyl adipate, dibutyl sebacate, tributyl phosphate, triphenyl phosphate, trioctyl phosphate, triethyl citrate, tributyl citrate, acetyl tributyl citrate, and diethylene glycol dibenzoate.

[0013] The second aspect of the present application provides the use of the method for detecting the migration amount of non-phthalate plasticizers in paper packaging products described in the first aspect in detecting non-phthalate plasticizers in paper packaging products.

[0014] The beneficial effects of this application are:

[0015] 1) By analyzing the characteristics of paper packaging materials, optimizing the pretreatment method, and screening suitable internal standards, a method was used to analyze multiple types of typical non-phthalate plasticizers (those used more frequently and at higher levels in paper packaging production are considered typical analytes in this patent). This method has fast analysis speed, high precision, and good accuracy. It can complete the simultaneous detection of 13 typical non-phthalate plasticizers in four categories within 16 minutes, and is suitable for rapid screening and analysis of large quantities of samples.

[0016] 2) By optimizing the split ratio and selecting an ion lens with a suitable aperture for the experiment, the linearity problem of the standard curve of non-ophthalic plasticizers in a wide concentration range was solved to meet the analysis requirements of different products in actual production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The display is the ion selective chromatogram of the standard working solution in the present invention, and the inset is the enlarged view of the substances numbered 2-4. Among them:

[0018] 1 is diethyl adipate (DEA); 2 is tributyl phosphate (TBP); 3 is triethyl citrate (TEC); 4 is diisobutyl adipate (DIBA); 5 is dibutyl adipate (DBA); 6 is dibutyl sebacate (DBS); 7 is tributyl citrate (TBC); 8 is acetyl tributyl citrate (ATBC); 9 is bis (2-butoxyethyl) adipate (BXA); 10 is diisooctyl adipate (DEHA); 11 is triphenyl phosphate (TPP); 12 is trioctyl phosphate (TOP); 13 is diethylene glycol dibenzoate (DEDB); 14 is benzyl benzoate (internal standard ISTD).

[0019] Figure 2 The figure shows the comparison of the extraction of 13 non-phthalate plasticizers by different solvents in the present invention.

[0020] Figure 3 Shown is a comparison chart of the extraction of 13 non-phthalate plasticizers at different extraction times in the present invention. DETAILED DESCRIPTION

[0021] 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.

[0022] 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.

[0023] 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.

[0024] This application proposes for the first time a method for detecting the migration of non-phthalate plasticizers in paper packaging products into dry simulants. By analyzing the characteristics of paper packaging materials, optimizing the pretreatment method, and screening suitable internal standards, a method is used to accurately detect multiple types of typical non-phthalate plasticizers. By optimizing the size of the split ratio and selecting an ion lens with a suitable aperture for the experiment, the linearity problem of the standard curve of non-phthalate plasticizers in a wide concentration range is solved.

[0025] The present application first provides a method for detecting the migration amount of non-phthalate plasticizers in paper packaging products, characterized in that the detection method comprises the following steps:

[0026] S1) performing a migration test on the paper packaging product to be tested and the dry simulant to obtain the dry simulant after migration;

[0027] S2) preparing a standard working solution, and preparing the migrated dry simulant obtained in S1) into a simulant solution to be tested; the standard working solution and the simulant solution to be tested include an internal standard;

[0028] S3) using a gas chromatography-mass spectrometer to detect the standard working solution and the simulant solution to be tested, and calculating the non-phthalate plasticizer content in the simulant solution to be tested according to the standard curve.

[0029] The paper packaging products are packaging items made of paper, cardboard or other paper products. Such products are widely used in the packaging of various commodities, such as food, beverages, cosmetics, medicines, electronic products, etc.

[0030] The migration of non-phthalate plasticizers in paper packaging refers to the amount of these plasticizers that migrate from paper packaging materials to substances that come into contact with them (which may be food, beverages, medicines, cosmetics, etc.). The migration amount is an important indicator because it can indicate whether the content of plasticizers in the packaging material may cause contamination to the substances in the packaging.

[0031] In a specific embodiment of the present application, the migration amount of non-phthalate plasticizer in the paper packaging product is the migration amount of the non-phthalate plasticizer in the paper packaging product into the dry simulant.

[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] In a specific embodiment of the present application, the non-phthalate plasticizer is selected from any one or more of diethyl adipate, diisobutyl adipate, dibutyl adipate, bis(2-butoxyethyl) adipate, diisooctyl adipate, dibutyl sebacate, tributyl phosphate, triphenyl phosphate, trioctyl phosphate, triethyl citrate, tributyl citrate, acetyl tributyl citrate, and diethylene glycol dibenzoate.

[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 benzyl benzoate.

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

[0036] In a specific embodiment of the present application, the solvent of the test simulant solution is selected from n-hexane, ethyl acetate, and isopropanol. In a preferred embodiment, the solvent of the standard working solution is n-hexane, which has the highest extraction efficiency for all target substances and more stable results.

[0037] In a specific embodiment of the present application, the internal standard is added in the form of an internal standard solution, and the concentration of the internal standard solution can be 0.5 μg / mL to 1.5 μg / mL, for example, 0.5 μg / mL, 0.6 μg / mL, 0.7 μg / mL, 0.8 μg / mL, 0.9 μg / mL, 1.0 μg / mL, 1.1 μg / mL, 1.2 μg / mL, 1.3 μg / mL, 1.4 μg / mL, 1.5 μg / mL.

[0038] In a specific embodiment of the present application, in the standard working solution, the amount of the internal standard solution added to the standard working solution is 40 μL-100 μL, for example, 40 μL, 50 μL, 60 μL, 70 μL, 80 μL, 90 μL, 100 μL. When the standard working solution is tested, under the above-mentioned internal standard conditions, it can maximize the accuracy and repeatability of the analysis, and compensate for the volume changes, injection volume changes, detector response changes, and degradation or loss of sample components that may occur during sample processing and analysis.

[0039] In a specific embodiment of the present application, in the test simulant solution, the amount of the internal standard solution added to the test simulant solution is 240 μL-300 μL, for example, 240 μL, 250 μL, 260 μL, 270 μL, 280 μL, 290 μL, 300 μL. When the test simulant solution is detected, under the above-mentioned internal standard conditions, the accuracy and repeatability of the analysis can be maximized, and the volume change, injection volume change, detector response change, and degradation or loss of sample components that may occur during sample processing and analysis can be compensated.

[0040] In a specific embodiment of the present application, the migration test is to place the paper packaging product to be tested in contact with a dry simulant in a closed container. Through the following contact conditions, the non-phthalate plasticizer in the paper packaging product to be tested can effectively migrate to the dry simulant, thereby ensuring the accuracy of the migration test.

[0041] In a specific embodiment of the present application, the contact placement temperature can be 30°C to 80°C, for example, it can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C. In certain embodiments of the present application, the contact placement temperature can be 40°C-60°C.

[0042] In a specific embodiment of the present application, the contact placement time can be 24h-240h; for example, it can be 24h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h, 120h, 130h, 140h, 150h, 160h, 170h, 180h, 190h, 200h, 210h, 220h, 230h, 240h. In certain embodiments of the present application, the contact placement time can be 192h-240h.

[0043] 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, 1g, 1.5g, 2g, 2.5g, 3g, 3.5g, 4g, 4.5g, or 5g.

[0044] In a specific embodiment of the present application, in the migration test, the area of ​​the paper packaging product to be tested can be 0.25 dm 2 -1.5dm 2 , for example, it can be 0.25dm 2 , 0.5dm 2 , 0.6dm 2 , 0.7dm 2 , 0.8dm 2 , 0.9dm 2 , 1.0dm 2 , 1.1dm 2 , 1.2dm 2 , 1.3dm 2 , 1.4dm 2 , 1.5dm 2 .

[0045] 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 product to be tested can be 4 to 20:1 g / dm 2 , for example, it can be 4:1 g / dm 2 , 5:1g / dm 2 , 6: 1g / dm 2 , 7: 1g / dm 2 , 8: 1g / dm 2 , 9:1g / dm 2 , 10:1g / dm 2 , 11:1g / dm 2 , 12:1g / dm 2 , 13:1g / dm 2 , 14:1g / dm 2 , 15:1g / dm 2 , 16:1g / dm 2 , 17:1g / dm 2 , 18:1g / dm 2 , 19:1g / dm 2 , 20:1g / dm 2 .

[0046] In the specific embodiment of the present application, the steps of the migration test are as follows: weigh 1g of MPPO and spread it evenly in a glass culture bottle, 2Place the inner liner paper on top of the MPPO (with the aluminum foil facing up), and then cut the 0.25dm 2 The outer packaging paper sample is placed on top of the inner liner paper (printed side facing up), and then the lid is closed and sealed. The petri dish is placed in an oven at 40°C for 10 days, and then taken out and cooled to room temperature.

[0047] In a specific embodiment of the present application, the standard working solution is a series of concentration gradient solutions of non-phthalate plasticizers; a series of concentration gradient solutions refers to a series of solutions with different concentrations, where the concentration increases or decreases according to a certain gradient, and is used to determine certain properties of a substance or perform quantitative analysis.

[0048] In a specific embodiment of the present application, the standard working solution is prepared according to the following method: accurately weigh 50 mg of the standard of each non-phthalate plasticizer, place it in a 50 mL volumetric flask, make up to volume with n-hexane, and prepare a mixed standard solution I with a concentration of 1.0 mg / mL; take the above mixed standard solution I, dilute it 10 times with n-hexane, and prepare a mixed standard solution II with a concentration of 0.1 mg / mL; accurately pipette 5 μL, 100 μL, 250 μL, 500 μL, and 2000 μL of the mixed standard solution II, respectively, and place it in a 10 mL volumetric flask, then accurately add 60 μL, 1.0 mg / mL internal standard, make up to volume with n-hexane, and obtain a standard working solution with a concentration range of 0.05 μg / mL-20 μg / mL.

[0049] In a specific embodiment of the present application, the concentration of the standard working solution can be 0.05 μg / mL-20.0 μg / mL, for example, 0.05 μg / mL, 1.0 μg / mL, 2.5 μg / mL, 5 μg / mL, 20 μg / mL.

[0050] In a specific embodiment of the present application, a standard curve is obtained by detecting non-phthalate plasticizers in a standard working solution. The standard curve uses the ratio of the quantitative ion peak area of ​​each non-phthalate plasticizer to the quantitative ion peak area of ​​the internal standard as the ordinate, and the content of the corresponding non-phthalate plasticizer as the abscissa. The linear correlation coefficient R of the standard curve obtained by optimizing the split ratio and selecting an ion lens with a suitable aperture is 2 All of them are greater than 0.998, indicating that the standard curve is a linear curve with a good linear relationship.

[0051] In a specific embodiment of the present application, the content of non-phthalate plasticizers in the simulant solution to be tested is calculated using the standard working curve and the ratio of the quantitative ion peak area of ​​the non-phthalate plasticizer corresponding to the simulant solution to the quantitative ion peak area of ​​the internal standard, which is the migration amount of non-phthalate plasticizers in the paper packaging.

[0052] In a specific embodiment of the present application, the method for preparing the simulated substance solution to be tested from the migrated dry simulated substance obtained in S1) is as follows: the simulated material obtained from the migration test is transferred to a container, a solvent and an internal standard are added for extraction, and then a simulated substance solution to be tested is obtained by separation.

[0053] In a specific embodiment of the present application, the container may be a centrifuge tube.

[0054] In a specific embodiment of the present application, in the test simulant solution, the ratio of the added volume of the solvent to the mass of the dry simulant can be 40-100:1 mL / g, for example, 40:1 mL / g, 50:1 mL / g, 60:1 mL / g, 70:1 mL / g, 80:1 mL / g, 90:1 mL / g, 100:1 mL / g.

[0055] In a specific embodiment of the present application, the extraction time can be 10 min to 60 min, for example, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min. In a preferred embodiment, the extraction time is 20 min. Under this extraction condition, the measured value data fluctuates the least and is the most stable.

[0056] In a specific embodiment of the present application, the rotation speed during extraction can be 200r / min to 1000r / min, for example, it can be 200r / min, 250r / min, 300r / min, 350r / min, 400r / min, 450r / min, 500r / min, 550r / min, 600r / min, 650r / min, 700r / min, 750r / min, 800r / min, 850r / min, 900r / min, 950r / min, 1000r / min.

[0057] In certain embodiments of the present application, the extraction can be carried out using a vortex oscillator, the working time of the vortex oscillator can be 10 minutes to 60 minutes, and the working speed of the vortex oscillator can be 200r / min to 1000r / min. Under these conditions, it is beneficial to extract non-phthalate plasticizers in the dry simulant sample solution to the greatest extent.

[0058] In a specific embodiment of the present application, the separation method adopts filtration membrane separation, which is conducive to complete separation of the solid phase and the liquid phase after extraction under the following conditions.

[0059] In a specific embodiment of the present application, the size of the filter membrane can be 0.2μm-1.0μm, for example, it can be 0.2μm, 0.22μm, 0.3μm, 0.4μm, 0.45μm, 0.5μm, 0.6μm, 0.7μm, 0.8μm, 0.9μm, 1.0μm. In a preferred embodiment of the present application, the size of the filter membrane can be 0.22μm-0.45μm.

[0060] In a specific embodiment of the present application, the chromatographic column of the gas chromatography is selected from a weakly polar DB-5 capillary column, a strongly polar DB-wax capillary column and a medium polarity DB-17 capillary column. In a preferred embodiment, the chromatographic column is an Agilent DB-5 capillary column with a model of 30m×0.25mm×0.25μm. When using this chromatographic column, the peak shape of the target substance is symmetrical, the separation effect is better, and it has a better response.

[0061] In a specific embodiment of the present application, the injection port temperature of the gas chromatograph can be 250°C to 300°C, for example, 250°C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C, or 300°C.

[0062] In a specific embodiment of the present application, the carrier gas of the gas chromatography is high-purity helium, and the purity of the helium is ≥99.999%.

[0063] In a specific embodiment of the present application, the flow rate of the gas chromatography can be 1 mL / min to 1.5 mL / min, for example, it can be 1 mL / min, 1.1 mL / min, 1.2 mL / min, 1.3 mL / min, 1.4 mL / min, 1.5 mL / min.

[0064] In a specific embodiment of the present application, the split ratio of the gas chromatography can be (20-100):1, for example, it can be 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1.

[0065] In a specific embodiment of the present application, the injection volume of the gas chromatography can be 0.5μL-1.5μL, for example, it can be 0.5μL, 0.6μL, 0.7μL, 0.8μL, 0.9μL, 1.0μL, 1.1μL, 1.2μL, 1.3μL, 1.4μL, 1.5μL.

[0066] In a specific embodiment of the present application, the temperature rising program of the gas chromatography can be an isocratic or gradient temperature rising program, and the temperature rising program is an initial temperature of 60°C, maintained for 1 minute, then increased to 240°C at a rate of 20°C / min, maintained for 1 minute, and then increased to 280°C at a rate of 2°C / min, maintained for 3 minutes.

[0067] In a specific embodiment of the present application, the ionization method of the mass spectrometer is an electron bombardment ion source.

[0068] In a specific embodiment of the present application, the aperture of the ion lens of the mass spectrometer can be 3mm-9mm, for example, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm. In certain embodiments of the present application, the aperture of the ion lens can be 3mm, 6mm, 9mm. In a preferred embodiment, the aperture of the ion lens is 9mm. The ion lens is a device that uses an electric field to focus or defocus an ion beam. The size of the ion lens directly affects the number and speed of ions passing through. The larger the diameter of the ion lens, the more ions it can gather and guide, so that the number of ions passing through per unit time will also increase accordingly, improving the efficiency and accuracy of mass spectrometry analysis and improving the linearity of the standard curve. When 9mm is selected for the experiment, the standard curves of all the substances detected are linear, and the linear correlation coefficients are all greater than 0.998, which is conducive to more accurate detection of non-phthalate plasticizers.

[0069] In a specific embodiment of the present application, the ionization energy of the mass spectrometer can be 70 eV.

[0070] In a specific embodiment of the present application, the ion source temperature of the mass spectrometer can be 250°C to 300°C, for example, 250°C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C, or 300°C.

[0071] In a specific embodiment of the present application, the quadrupole temperature of the mass spectrometer can be 130°C to 180°C, for example, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, or 180°C.

[0072] In a specific embodiment of the present application, the transmission line temperature of the mass spectrometer can be 250°C to 300°C, for example, 250°C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, 290°C, 295°C, or 300°C.

[0073] In a specific embodiment of the present application, the solvent delay of the mass spectrometer can be 2 min to 4 min, for example, 2 min, 3 min, or 4 min.

[0074] In a specific embodiment of the present application, the data acquisition mode of the mass spectrometer is an ion monitoring mode.

[0075] The present application also provides the use of the above-mentioned method for detecting the migration amount of non-phthalate plasticizers in paper packaging products in detecting non-phthalate plasticizers in paper packaging products.

[0076] In a specific embodiment of the present application, the use is specifically the migration amount of non-phthalate plasticizer of paper packaging products to the dry simulant.

[0077] 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.

[0078] The liquid chromatography and mass spectrometry conditions used in the liquid chromatography tandem mass spectrometry in the examples are:

[0079] The conditions for gas chromatography were:

[0080] Chromatographic column: Agilent DB-5 capillary column, model: 30m×0.25mm×0.25μm;

[0081] Inlet temperature: 300°C;

[0082] Carrier gas: high alcohol helium (purity ≥ 99.999%);

[0083] Flow rate: 1.2 mL / min;

[0084] Split ratio: 50:1;

[0085] Injection volume: 1.0 μL;

[0086] The programmed temperature conditions were as follows: initial temperature 60°C, maintained for 1 min, then increased to 240°C at a rate of 20°C / min, maintained for 1 min, and then increased to 280°C at a rate of 2°C / min, maintained for 3 min.

[0087] The mass spectrometry conditions were:

[0088] Ionization method: electron bombardment ion source (EI);

[0089] Ion lens aperture: 9mm;

[0090] Ionization energy: 70 eV;

[0091] Ion source temperature: 280°C;

[0092] Quadrupole temperature: 150℃;

[0093] Transmission line temperature: 280°C;

[0094] Solvent delay: 4min;

[0095] Monitoring method: ion monitoring mode (SIM).

[0096] The information of the 13 non-phthalate plasticizers and internal standards in the examples is shown in Table 1.

[0097] Table 1 Information of 13 non-phthalate plasticizers and internal standards

[0098]

[0099]

[0100] Example 1 Screening and Optimization of Pretreatment Conditions

[0101] 1) Column selection

[0102] The separation of 13 non-phthalate esters on three different polarity chromatographic columns was investigated: weak polarity DB-5 capillary column, strong polarity DB-wax capillary column and medium polarity DB-17 capillary column. The results showed that when separated by DB-wax capillary column, the target substance had a more serious tailing phenomenon, which affected the subsequent peak area integration and quantitative analysis; on the medium polarity DB-17, the chromatographic peaks of some substances could not be completely separated, which also affected the quantitative analysis results. When the weak polarity DB-5 column was used to analyze the target substance, the peak shape of the target substance was symmetrical, the separation effect was better, and it had better response. Therefore, the DB-5 chromatographic column was selected as the separation column.

[0103] 2) Selection of extraction solvent

[0104] The 13 non-phthalate substances are easily soluble in organic solvents. Three organic solvents, n-hexane, ethyl acetate, and isopropanol, were selected to extract the target substances in the samples and investigate the extraction efficiency of organic solvents. The results showed that n-hexane had the highest extraction efficiency for all target substances and the results were more stable, so n-hexane was selected as the extraction solvent for subsequent experiments.

[0105] 3) Extraction time optimization

[0106] If the extraction time is too short, the target substance cannot be completely extracted, while if the extraction time is too long, it will not only increase the analysis time, but also extract too many impurities. The target substances in the samples were extracted respectively, and the extraction efficiency of the target substances when the extraction time was 10, 20, 30, 40, and 50 minutes was investigated and comprehensively evaluated. The results showed that the measured value data fluctuation of 20 minutes was the smallest and the most stable, and the subsequent experiments were conducted with 20 minutes.

[0107] Example 2 Optimization of ion lens aperture size

[0108] Commercially available 3mm, 6mm, and 9mm ion lenses were used for the experiment.

[0109] When 3mm is selected for the experiment, TEC, DIBA, DBA, DBS, TBC, ATBC, BXA, DEHA,

[0110] The standard curves of TPP, TOP and DEDB show quadratic curves. If the current curve is used for fitting, the linear term correlation coefficient is 0.923, which is poor in linearity.

[0111] When 6mm is selected for the experiment, the standard curves of TBC, ATBC, BXA, DEHA, TPP, TOP, and DEDB show a quadratic curve phenomenon. If the current curve is used for fitting, the linear term correlation coefficient is 0.984, and the linearity is poor.

[0112] When 9mm was selected for the experiment, the standard curves of all 13 substances were linear, and the linear correlation coefficients were all greater than 0.998, so the 9mm ion lens was used for subsequent experiments.

[0113] Example 3 Establishing a standard curve

[0114] 1) Preparation of internal standard solution

[0115] Accurately weigh 50 mg of benzyl benzoate into a 50 mL volumetric flask, dissolve it with n-hexane, and shake well to obtain an internal standard solution with a concentration of 1 mg / mL.

[0116] 2) Preparation of standard working solution

[0117] Accurately weigh 50 mg of the standard of each non-phthalate plasticizer, place it in a 50 mL volumetric flask, make up to volume with n-hexane to prepare a mixed standard solution I with a concentration of 1.0 mg / mL; take the above mixed standard solution I, dilute it 10 times with n-hexane, and prepare a mixed standard solution II with a concentration of 0.1 mg / mL; accurately pipette 5 μL, 100 μL, 250 μL, 500 μL, and 2000 μL of the mixed standard solution II, respectively, place them in a 10 mL volumetric flask, then accurately add 60 μL, 1.0 mg / mL internal standard, make up to volume with n-hexane, and obtain standard working solutions with concentrations ranging from 0.05 μg / mL, 1.0 μg / mL, 2.5 μg / mL, 5 μg / mL, and 20 μg / mL.

[0118] Liquid chromatography-tandem mass spectrometry was used to detect the content of each non-phthalate plasticizer in the standard solution.

[0119] The content of each non-phthalate plasticizer in the standard solution was used as the horizontal axis, and the ratio of the quantitative ion peak area of ​​each non-phthalate plasticizer to the quantitative ion peak area of ​​the internal standard was used as the vertical axis. The detection limit and quantitative limit were investigated, as shown in Table 2.

[0120] It can be seen from Table 2 that the linear correlation coefficient R 2 All of them are greater than 0.998, indicating that the standard curve is a linear curve with good linear relationship. The detection limit of this method is 0.016μg / mL-0.170μg / mL, and the quantification limit is 0.053μg / mL-0.570μg / mL, indicating that the method in this application has high sensitivity.

[0121] Table 2 Migration test standard working curve

[0122]

[0123]

[0124] Example 4 Recovery and Precision Test

[0125] This example is a test on the recovery rate of non-phthalate plasticizers in dry simulants.

[0126] 1) Take 1 g of dry simulant polyphenylene ether (MPPO), add three standard solutions with concentrations of 0.8 μg / mL, 3 μg / mL, and 6 μg / mL, respectively, and set aside after drying. Prepare three samples for each concentration.

[0127] 2) Place the above spiked dry simulant in a 50mL centrifuge tube, accurately add 40mL of n-hexane solution and 240μL of internal standard solution, vortex for 20min (500r / min), let stand for 5min, filter through a 0.45μm filter membrane, and analyze. Determine the content of non-phthalate plasticizers, and calculate the recovery rate and precision of the method. The results are shown in Table 3.

[0128] Table 3 Migration test recovery and precision test results

[0129]

[0130] The results showed that the recovery rate of non-phthalate plasticizers was 86.15%-119.20%; the precision RSD was 0.58%-5.89%, indicating that the recovery rate and precision of the method in this application were good.

[0131] Example 5 Detection of Migration of Non-Phthalate Plasticizers in Paper Packaging

[0132] Weigh 1g of MPPO and spread it evenly in a glass culture bottle. 2 Place the inner liner paper on top of the MPPO (with the aluminum foil facing up), and then cut the 0.25dm 2 The outer packaging paper sample is placed on top of the inner lining paper (printed side facing up), and then the lid is sealed. The petri dish is placed in an oven at 40°C for 10 days, and then taken out and cooled to room temperature. The MPPO in the petri dish is transferred to a 50mL stoppered centrifuge tube, 40mL of n-hexane solution and 240μL of internal standard solution are accurately added, vortexed for 20min (500r / min), and after standing for 5min, GC-MS analysis is performed after filtering through a 0.45μm filter membrane.

[0133] The common migration amount and migration rate of non-phthalate plasticizers in outer packaging paper and inner lining paper were tested. The results are shown in Table 4, where NA means that the substance was not detected. From the data in the table, it can be seen that the main common migrant is acetyl tributyl citrate. The migration amount of this substance in different samples varies greatly. Even though there are no clear control measures at present, since this substance is used in large quantities in paper packaging, it needs to be paid close attention.

[0134] Table 4 Test results of migration of non-phthalate plasticizers in paper packaging products

[0135]

[0136] 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 amount of non-phthalate plasticizers in paper packaging products, characterized in that: The detection method comprises the following steps: S1) performing a migration test on the paper packaging product to be tested and the dry simulant to obtain the dry simulant after migration; S2) preparing a standard working solution, and preparing the migrated dry simulant obtained in S1) into a simulant solution to be tested; the standard working solution and the simulant solution to be tested include an internal standard; S3) using a gas chromatograph-mass spectrometer to detect the standard working solution and the simulant solution to be tested, and calculating the non-phthalate plasticizer content in the simulant solution to be tested according to the standard curve; in the gas chromatograph-mass spectrometer, the ion lens of the mass spectrometer is 3 to 9 mm.

2. The detection method according to claim 1, characterized in that: The non-phthalate plasticizer is selected from any one or more of diethyl adipate, diisobutyl adipate, dibutyl adipate, bis(2-butoxyethyl) adipate, diisooctyl adipate, dibutyl sebacate, tributyl phosphate, triphenyl phosphate, trioctyl phosphate, triethyl citrate, tributyl citrate, acetylcitrate, and diethylene glycol dibenzoate; And / or, the dry mimetic is MPPO; And / or, the internal standard is benzyl benzoate; And / or, the solvent of the standard working solution is n-hexane; And / or, the solvent of the test simulant solution is selected from n-hexane, ethyl acetate, and isopropanol; preferably, the solvent of the standard working solution is n-hexane.

3. The detection method according to claim 1, characterized in that: The internal standard may also include any one or more of the following features: a) the internal standard substance is added in the form of an internal standard solution, the concentration of the internal standard solution is 0.5 mg / mL-1.5 mg / mL; b) in the standard working solution, the amount of the internal standard solution added to the standard working solution is 40 μL-100 μL; c) In the test simulant solution, the amount of the internal standard solution added to the test simulant solution is 240 μL-300 μL.

4. The detection method according to claim 1, characterized in that: The migration test is performed by placing the paper packaging product to be tested in contact with a dry simulant in a sealed container.

5. The detection method according to claim 4, characterized in that: The migration test includes any one or more of the following features: (1) The contact temperature is 30° C.-80° C., and the contact time is 24 h-240 h; (2) The mass of the dry simulant is 0.5 g to 5 g; (3) The area of ​​the paper packaging product to be tested is 0.25 dm 2 -1.5dm 2 ; (4) The ratio of the mass of the dry simulant to the area of ​​the paper packaging to be tested is 4 to 20:1 g / dm 2 .

6. The detection method according to claim 1, characterized in that: The standard working solution is a series of concentration gradient solutions of non-phthalate plasticizers; preferably, the concentration of the standard working solution is 0.05 μg / mL-20.0 μg / mL; And / or, the standard curve has the ratio of the quantitative ion peak area of ​​each non-phthalate plasticizer to the quantitative ion peak area of ​​the internal standard as the ordinate, and the content of the corresponding non-phthalate plasticizer as the abscissa.

7. The detection method according to claim 1, characterized in that: The method of preparing the simulated substance solution to be tested from the migrated dry simulated substance obtained in S1) is as follows: the simulated material obtained from the migration test is transferred to a container, a solvent and an internal standard are added for extraction, and then the simulated substance solution to be tested is obtained by separation.

8. The detection method according to claim 7, characterized in that: The extraction time is 10min to 60min, and the rotation speed during extraction is 200r / min to 1000r / min; And / or, the separation method adopts filter membrane separation, preferably, the size of the filter membrane is 0.2μm-1.0μm.

9. The detection method according to claim 1, characterized in that: The gas chromatograph mass spectrometer has one or more of the following features: 1) The chromatographic column of gas chromatography is selected from DB-5 capillary column, DB-wax capillary column and DB-17 capillary column; preferably, the chromatographic column is DB-5 capillary column; 2) The injection port temperature of the gas chromatograph is 250°C-300°C; 3) The carrier gas of gas chromatography is high-purity helium, and the purity of helium is ≥99.999%; 4) The flow rate of gas chromatography is 1 mL / min to 1.5 mL / min; 5) The split ratio of gas chromatography is 20 to 100:1; 6) The injection volume of gas chromatography is 0.5μL-1.5μL; 7) The temperature program of the gas chromatography is a gradient temperature increase; preferably, the temperature increase program is an initial temperature of 60°C, maintained for 1 min, then increased to 240°C at a rate of 20°C / min, maintained for 1 min, and then increased to 280°C at a rate of 2°C / min, Keep for 3 minutes; 8) The ionization mode of mass spectrometry is electron bombardment ion source; 9) The ion source temperature of the mass spectrometer is 250℃-300℃; 10) The quadrupole temperature of the mass spectrometer is 130℃-180℃; 11) The transmission line temperature of the mass spectrometer is 250℃-300℃; 12) The solvent delay of mass spectrometry is 2min to 4min; 13) The data acquisition mode of mass spectrometry is ion monitoring mode.

10. Use of the method for detecting the migration amount of non-phthalate plasticizers in paper packaging products according to any one of claims 1 to 9 in detecting non-phthalate plasticizers in paper packaging products.

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