CN115326992A - Method for detecting influence of different migration ways on inner lining paper barrier property - Google Patents

Method for detecting influence of different migration ways on inner lining paper barrier property Download PDF

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CN115326992A
CN115326992A CN202211073099.9A CN202211073099A CN115326992A CN 115326992 A CN115326992 A CN 115326992A CN 202211073099 A CN202211073099 A CN 202211073099A CN 115326992 A CN115326992 A CN 115326992A
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paper
lining paper
temperature
migration
inner lining
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Inventor
虞桂君
李登科
吴秉宇
王兵
谢雯燕
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Shanghai Tobacco Group Co Ltd
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Shanghai Tobacco Group Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G01N30/7206—Mass spectrometers interfaced to gas chromatograph
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N2030/0075—Separation due to differential desorption
    • G01N2030/008—Thermal desorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N2030/042—Standards
    • G01N2030/045—Standards internal

Abstract

The invention relates to a method for detecting the influence of different migration paths on the barrier property of lining paper, which comprises the following steps: 1) Inner lining paper migration and blocking experiments: an inner lining paper and trademark base paper are arranged in a device in a stacking mode from bottom to top; the bottom of the lining paper is provided with an adsorption layer; dripping standard solution on the trademark base paper, quickly sealing and inverting the device to ensure that the lining paper is fully contacted with the adsorption layer, and transferring at constant temperature in an inverted state to provide a transferred adsorption layer; wherein the inner lining paper comprises one or more of complete inner lining paper, creased inner lining paper and gapped inner lining paper; 2) And (3) detection: adding an internal standard solution into the adsorption layer after the migration provided by the step 1) for thermal desorption-gas chromatography-mass spectrometry detection. The method is simple to operate, and the result is visual and effective; the invention is suitable for detecting various different types of lining paper and has wide applicability.

Description

Method for detecting influence of different migration ways on inner lining paper barrier property
Technical Field
The invention relates to the technical field of liner paper performance detection, in particular to a method for detecting influences of different migration paths on barrier performance of liner paper.
Background
Some compounds in the cigarette label paper, such as residual solvents, additives, auxiliaries and the like, may migrate into tobacco shreds in the processes of packaging, storing and transporting, and influence the quality of cigarettes.
In the small cigarette case, the label paper is not in direct contact with the cigarette, and the lining paper is positioned between the label paper and the cigarette, so that the migration of some compounds in the label paper to the cut tobacco can be effectively prevented. However, the lining paper package is not in a completely sealed state, and the compound in the label paper may not only permeate through the lining paper and enter the cut tobacco through permeation, but also migrate through creases, gaps and the like on the lining paper and enter the cut tobacco, so that the migration barrier performance of the lining paper is reduced. A method for measuring the influence of different migration ways (permeation, crease and gap) on the migration blocking performance of the lining paper is established, quantitative basis is obtained, theoretical basis can be provided for the lining paper packaging design of the cigarette small box, the migration blocking effect of the lining paper packaging is improved, the migration risk of the trademark paper is reduced, and the quality of cigarette products are ensured.
Disclosure of Invention
In view of the above disadvantages of the prior art, in order to make up for the technical gap of the method for detecting the influence of different migration paths on the migration barrier performance of the lining paper in the prior art, the present invention aims to provide a method for detecting the influence of different migration paths on the barrier performance of the lining paper, which is used for solving the problems in the prior art.
To achieve the above and other related objects, the present invention provides a method for detecting the influence of different migration paths on the barrier property of lining paper, the method comprising the steps of:
1) Inner lining paper migration and obstruction experiment: an inner lining paper and trademark base paper are arranged in a device in a stacking mode from bottom to top; the bottom of the lining paper is provided with an adsorption layer; dripping standard solution on the trademark base paper, rapidly sealing and inverting a device containing the adsorption layer, the lining paper and the trademark base paper, fully contacting the lining paper with the adsorption layer, and transferring at constant temperature in an inverted state to provide a transferred adsorption layer; wherein the inner lining paper comprises one or more of a complete inner lining paper, a creased inner lining paper and a gapped inner lining paper;
2) And (3) detection: adding an internal standard solution into the adsorption layer after the migration provided by the step 1) for thermal desorption-gas chromatography-mass spectrometry detection.
In some embodiments of the present invention, in step 1), the apparatus comprises a base and a cover body capable of covering the base; a cavity is arranged in the base, and the adsorption layer is arranged at the bottom of the cavity; the lining paper cover is arranged on the upper surface of the base and then fixed; lay label paper body paper on interior slip sheet, and add standard solution on the label paper body paper, invert behind closing the base with the lid for interior slip sheet and adsorbed layer fully contact, keep transferring under the constant temperature of inversion state, in order to provide the adsorbed layer after the migration.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a specific method for determining the influence of different migration paths (permeation, creases and gaps) on the barrier property of the lining paper for the first time, and the method is simple to operate and has visual and effective results.
2. The invention can determine the migration blocking performance of the lining paper to different compounds, such as water, inorganic elements, volatile semi-volatile organic compounds, non-volatile organic compounds and the like according to actual needs, and has wide applicability.
3. The invention is suitable for detecting various lining papers of different types, such as composite aluminum foil linings, aluminum-plated linings, artistic linings and the like, is not limited by the lining paper process, and has wide applicability.
Drawings
FIG. 1 is a schematic view of a transfer device according to the present invention.
Description of the element reference numerals:
1. cover body
2. Sealing ring
3. Base seat
4. Fixing piece
5. Hollow cavity
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention is further described with reference to the following embodiments. It should be understood that the examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the following examples are given by way of illustration and are intended to demonstrate the efficacy and efficacy of the present invention as would be apparent to one skilled in the art from the disclosure herein.
Through a great deal of research and research, the inventor of the invention uses the same lining paper with integrity, crease and gap as the migration barrier material, uses the adsorbent to carry out migration experiments, compares and analyzes the content of adsorbed compounds, and judges the influence of different migration ways such as permeation, crease, gap and the like on the barrier performance of the lining paper. The present invention has been completed on the basis of this finding.
The invention provides a method for detecting the influence of different migration paths on the barrier property of lining paper, which comprises the following steps:
1) Inner lining paper migration and blocking experiments: an inner lining paper and trademark base paper are arranged in a device in a stacking mode from bottom to top; the bottom of the lining paper is provided with an adsorption layer; dripping standard solution on the trademark base paper, quickly sealing and inverting the device to ensure that the lining paper is fully contacted with the adsorption layer, and transferring at constant temperature in an inverted state to provide a transferred adsorption layer; wherein the inner lining paper comprises one or more of complete inner lining paper, creased inner lining paper and gapped inner lining paper;
2) And (3) detection: adding an internal standard solution into the adsorption layer after the migration provided by the step 1) for thermal desorption-gas chromatography-mass spectrometry detection.
In an embodiment of the present invention, the device in step 1) may be, for example, rectangular, and other shapes of devices may satisfy the migration experiment of the present invention, and are within the scope of the present invention.
Before inversion, the bottom of interior slip sheet is equipped with the adsorbed layer, interior slip sheet with the adsorbed layer separates the space contactless and places. When the device is inverted, the device comprises the adsorption layer, the lining paper and the trademark base paper.
In an embodiment of the present invention, in step 1), the inner liner paper with the fold is folded in half along a long side and then unfolded to form the fold. The shape of the inner liner paper may be, for example, a rectangle, and the long side is the long side of the rectangle. Preferably, the length of the lining paper is 13 to 15cm, and the width is 9 to 11cm. The lining paper with the gaps is formed by overlapping two rectangular lining papers with the same size along the long edge for a certain width, so that the gaps are formed in the overlapping area. Preferably, the length of the rectangular inner lining paper is 13-15 cm, the width is 5-6 cm, and the overlapped width is 0.8-1.2 cm. The lining paper is selected from all kinds of lining paper such as a composite aluminum foil lining, an aluminum-plated lining, an artistic lining, a parchment paper lining, a kraft paper lining and the like. The trademark base paper is selected from white cardboard and coated paper, and can be square, and the side length of the square is 5-6 cm.
In step 1), the device comprises a base 3 and a cover body 1 which can cover the base; a cavity 5 is arranged in the base, and the adsorption layer is arranged at the bottom of the cavity; the lining paper cover is arranged on the upper surface of the base and then fixed; lay label paper body paper on interior slip sheet, and add standard solution on the label paper body paper, invert behind closing the base with the lid for interior slip sheet and adsorbed layer fully contact, keep transferring under the constant temperature of inversion state, in order to provide the adsorbed layer after the migration. The cover body is quickly covered on the base after the standard solution is dripped, so that the standard solution is prevented from volatilizing, and the migration efficiency is improved.
In the embodiment of the present invention, the device further includes a sealing ring 2 and a fixing member 4, when the lining paper covers the upper surface of the base 3, the sealing ring 2 is placed on the lining paper, the cover body 1 is covered, and the fixing member 4 is used for fixing. And during fixation, the lining paper is kept between the trademark base paper and the adsorption layer. The fixing member 4 may be a screw, for example, and screw holes matched with the screw are provided on the cover 1, the sealing ring 2, and the base 3.
In the specific embodiment of the invention, the base 3 is matched with the cover body 1, so that the sealing performance of the device is greatly improved, and the escape of substances in the device and the interference of the external environment in a migration experiment can be avoided; meanwhile, the sealing ring 2 ensures that the lining paper is in contact with the single side of the adsorption layer, and the problem that substances added in the base paper of the label paper indirectly migrate into the adsorption layer through the edge gap of the device to influence the accuracy of a detection result is effectively avoided.
In the step 1), the adsorption layer is selected from an adsorbent; preferably, the adsorbent is selected from modified polyphenylene ether MPPO. When the device is inverted the lining paper with when the adsorption layer contacts, the device can be gently shaken, so that MPPO is uniformly distributed. MPPO can be, for example, the model number available from the manufacturer Supelco
Figure BDA0003830043580000031
TA 60/80 mesh.
In step 1) of the present invention, the standard solution is an alcohol solution of one or more selected from benzene, toluene, styrene, ethyl acetate, n-propyl acetate, n-butyl acrylate, isooctyl acetate, and isooctyl acrylate. Preferably, the alcohol solution is a methanol solution.
In a specific embodiment of the invention, the concentration of the standard solution is 20 to 500. Mu.g/mL. Preferably, the concentration of the standard solution is 20 to 50. Mu.g/mL, 50 to 100. Mu.g/mL, 100 to 200. Mu.g/mL, 200 to 500. Mu.g/mL, or the like.
In a specific embodiment of the present invention, the standard solution is added in an amount of 20 to 50. Mu.L. Preferably, the standard solution is added in an amount of 20 to 30. Mu.L, 30 to 40. Mu.L, 40 to 50. Mu.L, or the like.
In step 1) of the invention, the internal standard solution is an alcoholic solution of benzyl acetate. Preferably, the alcohol solution is a methanol solution.
In a specific embodiment of the invention, the addition amount of the internal standard solution is 1 to 2 μ L per 180mg of the adsorption layer. The concentration of the internal standard solution is 10-20 mug/mL. Preferably, the concentration of the internal standard solution is 10 to 12. Mu.g/mL, 12 to 15. Mu.g/mL, 15 to 18. Mu.g/mL, 18 to 20. Mu.g/mL, or the like. And after the internal standard solution is prepared, storing for later use.
In the step 1), the constant temperature is 40-60 ℃. Preferably, the constant temperature is 40 ℃, 50 ℃, 60 ℃ or the like. The migration time is 235-245 h. Preferably, the time for the migration is 239 to 241 hours. Migration at constant temperature is beneficial to the stability of the sample. More preferably, when the constant temperature is 40 ℃, the migration time is 240h; when the constant temperature is 50 ℃, the migration time is 240h; when the constant temperature is 60 ℃, the migration time is 240h. The time and temperature are combined and matched, so that the conditions of storing more than 30d, 30d-180d and 180d at room temperature can be simulated respectively, and the method has actual reference value.
In an embodiment of the present invention, after the migration experiment is completed, the device is taken out from the constant temperature state, the lining paper and the trademark base paper in the device are taken out, and the sample to be measured for MPPO is transferred to a sample bottle, preferably a glass sample bottle. The sample bottle is sealed and is subjected to vortex oscillation for 0.5-1 min at the rotating speed of 2000-2500 r/min, and the vortex oscillation is beneficial to fully mixing the transferred MPPO, so that the sampling is more uniform.
In the method for detecting the influence of different migration paths on the barrier property of the lining paper, the step 2) is to detect: adding an internal standard solution into the transferred adsorption layer provided in the step 1) for thermal desorption-gas chromatography-mass spectrometry detection.
In step 2), the thermal desorption conditions for the thermal desorption-gas chromatography-mass spectrometry combined detection are as follows:
desorption temperature: 260 to 280 ℃; preferably 260 to 270 ℃ and 270 to 280 ℃.
Desorption time: 9-11 min; preferably 9 to 10min,10 to 11min, etc.
Cold trap temperature: trapping at 3-5 deg.c; preferably 3 to 4 ℃, 4 to 5 ℃ and the like; desorbing at 270-290 deg.c; preferably 270 to 280 ℃ and 280 to 290 ℃.
Transmission line temperature: 240-260 ℃; preferably 240 to 250 ℃ and 250 to 260 ℃.
Valve temperature: 240-260 ℃; preferably 240 to 250 ℃ and 250 to 260 ℃.
Inlet desorption flow: 35-45 mL/min; preferably 35 to 40mL/min, 40 to 45mL/min, etc.
Inlet split flow: 25-30 mL/min; preferably 25 to 27mL/min, 27 to 30mL/min, etc.
Outlet inlet chromatographic column flow: 1.5-2.5 mL/min; preferably 1.5 to 2mL/min, 2 to 2.5mL/min, etc.
And (3) outlet flow splitting flow: 9-11 mL/min; preferably 9 to 10mL/min, 10 to 11mL/min, etc.
In step 2), the conditions of the gas chromatograph for thermal desorption-gas chromatography-mass spectrometry detection are as follows:
a chromatographic column: DB-WAX [60m (length) × 0.32 μm (inner diameter) × 0.25 μm (film thickness) ];
carrier gas: helium with the purity of more than or equal to 99.999 percent;
temperature programming conditions: the initial temperature is 35-45 ℃, the temperature is kept for 5-6 min, the temperature is raised to 120-125 ℃ at the speed of 3-4 ℃/min, then the temperature is raised to 200-210 ℃ at the speed of 25-30 ℃/min, and the temperature is kept for 5-6 min.
In step 2), the conditions of the mass spectrometer for thermal desorption-gas mass spectrometry detection are as follows:
electron ionization source: EI;
ionization voltage: 69-71 eV; preferably 69 to 70eV, 70 to 71eV, or the like.
Transmission line temperature: 220 to 240 ℃; preferably 220 to 230 ℃ and 230 to 240 ℃ and the like.
Ion source temperature: 220 to 240 ℃; preferably 220 to 230 ℃ and 230 to 240 ℃ and the like.
Quadrupole temperature: 145 to 155 ℃; preferably 145 to 150 ℃ and 150 to 155 ℃.
Solvent retardation: 3-4 min; preferably 3 to 3.5min, 3.5 to 4min, etc.
Detection mode: and the total ion flow diagram of the full scanning is qualitative, and the selected ion monitoring mode is quantitative.
In some embodiments of the present invention, the migration barrier performance of the liner paper in the semi-quantitative detection result can be represented by a response value ratio, and the response value ratio is calculated by the following formula: response value ratio = response value of standard compound/response value of internal standard substance in adsorption layer after migration. The smaller the number, the better the migration barrier properties of the inner liner paper.
In some embodiments of the present invention, the migration barrier performance of the liner paper in the quantitative detection result can be expressed by a migration rate, and the calculation formula of the migration rate is as follows: mobility = (content of standard compound in adsorption layer after migration/content of standard compound added in base paper of trademark) × 100%. The smaller the number, the better the migration barrier properties of the inner liner paper. The quantitative method comprises the steps of preparing a series of standard working solutions with gradient concentrations, heating and gasifying the series of standard working solutions with gradient concentrations and the internal standard solution, introducing the series of standard working solutions with gradient concentrations and the internal standard solution into a commercial thermal desorption tube filled with the MPPO adsorbent, and then carrying out thermal desorption-gas mass spectrometry detection. And drawing a standard curve by taking the concentration of a standard compound in the standard working solution as a horizontal coordinate and taking the ratio of the quantitative ion peak area of the standard compound to the internal standard as a vertical coordinate. And substituting the detection result of the transferred adsorption layer into the standard curve to calculate the content of the standard compound in the transferred adsorption layer.
In the method for detecting the influence of different migration paths on the migration blocking performance of the lining paper, the same lining paper which is complete and provided with the crease and the gap is used as the migration blocking material, the migration experiment is carried out by using the adsorbent, and the content of the adsorbed standard compound is contrastively analyzed, so that the influence of different migration paths such as the permeation, the crease, the gap and the like on the migration blocking performance of the lining paper is judged.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a specific method for determining the influence of different migration paths (permeation, creases and gaps) on the barrier property of the lining paper for the first time, and the method is simple to operate and has visual and effective results.
2. The invention can determine the migration blocking performance of the lining paper to different compounds, such as water, inorganic elements, volatile semi-volatile organic compounds, non-volatile organic compounds and the like according to actual needs, and has wide applicability.
3. The invention is suitable for detecting various lining papers of different types, such as composite aluminum foil linings, aluminum-plated linings, artistic linings and the like, is not limited by the lining paper process, and has wide applicability.
The invention of the present application is further illustrated by the following examples, which are not intended to limit the scope of the present application.
Wherein MPPO is available from Supelco
Figure BDA0003830043580000061
TA 60/80 mesh.
Example 1
Quantitatively measuring the migration and barrier performance of three different types of lining paper (aluminized lining paper, composite aluminum foil lining paper and double-aluminum lining paper) with integrity, creases and gaps on benzene, toluene and styrene in the label paper. The experimental procedure was as follows:
a. preparation of paper samples: selecting 3 different process lining papers, namely aluminized lining paper, composite aluminum foil lining paper and double-aluminum lining paper, and cutting the aluminized lining paper, the composite aluminum foil lining paper and the double-aluminum lining paper into rectangles of 14cm multiplied by 10cm for later use; cutting white cardboard (trademark paper base paper) into 5cm × 5cm square for later use.
b. Preparing a standard working solution: methanol is used as a solvent to prepare 5-grade standard solutions with equal concentration of benzene, toluene and styrene, the concentration is respectively 20, 50, 100, 200 and 500 mu g/mL, and the standard solutions are stored at 4 ℃ for standby.
c. Preparing an internal standard solution: methanol is used as a solvent to prepare a methanol solution of benzyl acetate with the concentration of 10 mu g/mL, and the solution is preserved at 4 ℃ for standby.
d. Migration experiment: weighing 1.0g (accurate to 0.001 g) of clean MPPO, uniformly paving in a cavity of a base of a migration device, respectively covering a complete lining paper pattern with creases and gaps on the base, pressing a sealing ring, stacking 5cm multiplied by 5cm trademark paper base paper (with a rough surface facing upwards) at the middle position of the lining paper, accurately transferring 20 mu L of benzene, toluene and styrene standard solution with the concentration of 200 mu g/ml to the trademark paper base paper, quickly covering a cover body, and screwing and sealing screws. And then inverting the whole device by 180 degrees, enabling the MPPO to be in direct contact with lining paper, slightly and horizontally shaking the device to enable the MPPO to be uniformly distributed, keeping the device in an inverted state, and integrally placing the device in a thermostat at 40 ℃ for transferring for 240 hours.
e. MPPO sample detection: transferring the transferred MPPO sample into a clean sample bottle, sealing, uniformly mixing for 0.5min in a vortex mode at the speed of 2000r/min, then accurately weighing 180mg (accurate to 0.1 mg), filling the mixture into a clean glass thermal desorption sample tube, introducing 1 mu L of internal standard solution and 1 mu L of methanol into the sample tube by heating and gasifying, and then carrying out thermal desorption-gas chromatography-mass spectrometry detection, wherein the instrument conditions are as follows. (1) thermal desorption conditions: the desorption temperature is 270 ℃; the desorption time is 10min; cold trap temperature 4 deg.c (trapping) and 280 deg.c (desorbing); the transmission line temperature is 250 ℃; valve temperature: 250 ℃; the inlet desorption flow is 40mL/min; the inlet split flow is 27mL/min; the flow rate of the liquid entering the chromatographic column from the outlet is 2mL/min; the outlet split flow rate is 10mL/min. (2) gas chromatograph conditions: column DB-WAX [60m (length) × 0.32 μm (inner diameter) × 0.25 μm (film thickness) ]; the carrier gas is helium (the purity is more than or equal to 99.999%); temperature programming conditions: the initial temperature was 40 deg.C, held for 5min, ramped up to 120 deg.C at a rate of 4 deg.C/min, ramped up to 200 deg.C at a rate of 30 deg.C/min, and held for 5min. (3) mass spectrometer conditions: an electron ionization source (EI); ionization voltage 70eV; the transmission line temperature is 230 ℃; the ion source temperature is 230 ℃; the temperature of a four-level bar is 150 ℃; delaying the solvent for 3min; detection mode: total ion flow graph (TIC) qualitative of full scan, select ion monitoring mode (SIM) quantitative; retention time and mass spectral parameters for the standard compound and internal standard are shown in table 1.
TABLE 1 Retention time and Mass Spectrometry parameters for Standard Compounds and internal standards
Figure BDA0003830043580000071
f. Drawing a standard curve: aging the MPPO commercial glass thermal desorption tube, and mixing 1 μ L of each level of standard working solution (step b) and 1 μ L of the working solutionThe target solution was introduced into the sample solution by heating and vaporizing, and then the measurement was carried out under the conditions of the apparatus of step e. Drawing a standard curve by taking the concentration of each level of standard working solution as a horizontal coordinate and the ratio of the quantitative ion peak area of the standard compound to the internal standard as a vertical coordinate to obtain a linear regression equation and a correlation coefficient of benzene, toluene and styrene, and the correlation coefficient R 2 Are all larger than 0.999.
g. And (4) conclusion: and substituting the measured contents of benzene, toluene and styrene in the MPPO sample after migration and the content of the added standard compound in the base paper of the trademark paper into a formula for calculation to obtain the mobilities of benzene, toluene and styrene, wherein the mobility is = (the content of the standard compound in the adsorption layer after migration/the content of the standard compound added in the base paper of the trademark) × 100%. The smaller the number, the better the migration barrier properties of the liner paper. The details are shown in Table 2 below. As can be seen from the data in the table, the barrier properties of the liner paper affect: gaps are larger than creases and larger than permeation, the lining paper has different blocking performance in different processes, and the migration blocking performance of the double-aluminum lining paper is optimal.
Table 2 results of mobility measurements
Figure BDA0003830043580000072
Figure BDA0003830043580000081
Example 2
And (3) semi-quantitatively determining the migration barrier performance of the complete aluminum-plated lining paper with the crease and the gap to ethyl acetate, n-propyl acetate, n-butyl acrylate, isooctyl acetate and isooctyl acrylate in the label paper. The experimental procedure was as follows:
a. preparation of a paper sample: cutting the aluminized lining paper into a rectangle of 14cm multiplied by 10cm for later use; the white cardboard (trademark paper base paper) is cut into 5cm multiplied by 5cm square for standby.
b. Preparing a standard solution: using methanol as solvent to prepare 100 mug/mL standard solution of ethyl acetate, n-propyl acetate, n-butyl acrylate, isooctyl acetate and isooctyl acrylate, and storing at 4 deg.C.
c. Preparing an internal standard solution: a10. Mu.g/mL solution of benzyl acetate in methanol was prepared using methanol as the solvent and stored at 4 ℃ until use.
d. Migration experiment: weighing 1.0g (accurate to 0.001 g) of clean MPPO, uniformly paving in a cavity of a base of a migration device, respectively covering a complete lining paper pattern with creases and gaps on the base, pressing a sealing ring, stacking 5cm multiplied by 5cm trademark paper base paper (with a rough surface facing upwards) at the middle position of the lining paper, accurately transferring 100 mu g/mL standard solutions of 50 mu L of ethyl acetate, n-propyl acetate, n-butyl acrylate, isooctyl acetate and isooctyl acrylate, dripping the standard solutions onto the trademark paper base paper, quickly covering a cover body, and screwing screws for sealing. And then inverting the whole device by 180 degrees, enabling the MPPO to be in direct contact with lining paper, slightly and horizontally shaking the device to enable the MPPO to be uniformly distributed, keeping the device in an inverted state, and integrally placing the device in a thermostat at 40 ℃ for transferring for 240 hours.
e. MPPO sample detection: transferring the transferred MPPO sample into a clean sample bottle, sealing, uniformly mixing for 0.5min in a vortex mode at the speed of 2000r/min, then accurately weighing 180mg (accurate to 0.1 mg), filling the mixture into a clean glass thermal desorption sample tube, introducing 1 mu L of internal standard solution and 1 mu L of methanol into the sample tube by heating and gasifying, and then carrying out thermal desorption-gas chromatography-mass spectrometry detection, wherein the instrument conditions are as follows. (1) thermal desorption conditions: the desorption temperature is 270 ℃; the desorption time is 10min; the cold trap temperature is 4 ℃ (trapping) and 280 ℃ (desorption); the transmission line temperature is 250 ℃; valve temperature: 250 ℃; the inlet desorption flow is 40mL/min; the inlet flow rate of the split flow is 27mL/min; the flow rate of the outlet entering the chromatographic column is 2mL/min; the outlet split flow rate is 10mL/min. (2) gas chromatograph conditions: column DB-WAX [60m (length) × 0.32 μm (inner diameter) × 0.25 μm (film thickness) ]; the carrier gas is helium (the purity is more than or equal to 99.999%); temperature programming conditions: the initial temperature was 40 deg.C, held for 5min, ramped up to 120 deg.C at a rate of 4 deg.C/min, ramped up to 200 deg.C at a rate of 30 deg.C/min, and held for 5min. (3) mass spectrometer conditions: an electron ionization source (EI); ionization voltage 70eV; the transmission line temperature is 230 ℃; the ion source temperature is 230 ℃; the temperature of a four-level bar is 150 ℃; delaying the solvent for 3min; detection mode: the total ion flow map (TIC) for a full scan is qualitative, and the ion monitoring mode (SIM) is selected for quantification. The retention times and mass spectral parameters of the standard compounds and internal standards are shown in table 3.
TABLE 3 Retention time and Mass Spectrometry parameters for Standard Compounds and internal standards
Figure BDA0003830043580000091
f. And (4) conclusion: the ratio of the response values of the standard compound to the internal standard compound was used as a semi-quantitative result, which is shown in Table 4 below. The data in the table show that when the aluminized lining paper is complete, the ester compound in the base paper of the trademark paper can be effectively blocked, but when the aluminized lining paper has creases and particularly gaps, the migration blocking performance of the lining paper is obviously reduced.
TABLE 4 ratio of response values of standard compound to internal standard
Figure BDA0003830043580000092
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. A method of detecting the effect of different migration pathways on liner paper barrier performance, the method comprising the steps of:
1) Inner lining paper migration and obstruction experiment: an inner lining paper and trademark base paper are arranged in a device in a stacking mode from bottom to top; the bottom of the lining paper is provided with an adsorption layer; dripping standard solution on the trademark base paper, quickly sealing and inverting the device to ensure that the lining paper is fully contacted with the adsorption layer, and transferring at constant temperature in an inverted state to provide a transferred adsorption layer; wherein the inner lining paper comprises one or more of complete inner lining paper, creased inner lining paper and gapped inner lining paper;
2) And (3) detection: adding an internal standard solution into the adsorption layer after the migration provided by the step 1) for thermal desorption-gas chromatography-mass spectrometry detection.
2. The method of claim 1, wherein in step 1), the inner lining paper with the creases is folded along the long edges and then unfolded to make the creases; preferably, the length of the lining paper is 13-15 cm, and the width of the lining paper is 9-11 cm;
and/or the lining paper with the gaps is formed by overlapping two rectangular lining papers with the same size along the long edge for a certain width, so that the gaps are formed in the overlapping area; preferably, the length of the rectangular inner lining paper is 13-15 cm, the width is 5-6 cm, and the overlapped width is 0,8-1.2 cm.
3. The method of claim 1, wherein the liner paper is selected from all kinds of liner paper such as a composite aluminum foil liner, an aluminum plated liner, an artistic liner, a parchment paper liner, a kraft paper liner, and the like.
4. The method according to claim 1, wherein in step 1), the device comprises a base (3) and a cover (1) which can be covered on the base; a cavity (5) is arranged in the base, and the adsorption layer is arranged at the bottom of the cavity; the lining paper cover is arranged on the upper surface of the base and then fixed; lay the label paper body paper on the interior slip sheet, and add standard solution on the label paper body paper, invert behind the lid closes the base for interior slip sheet and adsorbed layer fully contact, keep transferring under the constant temperature of the state of inverting, in order to provide the adsorbed layer after the migration.
5. The method of claim 1, wherein in step 1), the adsorbent layer is selected from an adsorbent; preferably, the adsorbent is selected from modified polyphenylene ether and/or activated carbon.
6. The method of claim 1, wherein in step 1), the standard solution is selected from an alcohol solution of one or more of benzene, toluene, styrene, ethyl acetate, n-propyl acetate, n-butyl acrylate, isooctyl acetate, and isooctyl acrylate;
and/or the concentration of the standard solution is 20-500 mug/mL;
and/or the addition amount of the standard solution is 20-50 mu L;
and/or the internal standard solution is an alcoholic solution of benzyl acetate;
and/or the addition amount of the internal standard solution is 1-2 mu L per 180mg of the adsorption layer.
7. The method of claim 1, wherein the constant temperature is 40-60 ℃ in step 1); the migration time is 235-245 h.
8. The method according to claim 1, wherein in step 2), the thermal desorption conditions for the thermal desorption-gas mass spectrometry are as follows:
desorption temperature: 260 to 280 ℃;
desorption time: 9-11 min;
cold trap temperature: trapping at 3-5 deg.c and desorbing at 270-290 deg.c;
transmission line temperature: 240-260 ℃;
valve temperature: 240-260 ℃;
inlet desorption flow: 35-45 mL/min;
inlet split flow: 25-30 mL/min;
outlet inlet chromatographic column flow: 1.5-2.5 mL/min;
and (3) outlet flow splitting flow: 9-11 mL/min.
9. The method of claim 1, wherein in the step 2), the conditions of the gas chromatograph for thermal desorption-gas chromatography-mass spectrometry detection are as follows:
a chromatographic column: DB-WAX [60m (length) × 0.32 μm (inner diameter) × 0.25 μm (film thickness) ];
carrier gas: helium with purity more than or equal to 99.999%;
temperature programming conditions: the initial temperature is 35-45 ℃, the temperature is kept for 5-6 min, the temperature is increased to 120-125 ℃ at the speed of 3-4 ℃/min, then the temperature is increased to 200-210 ℃ at the speed of 25-30 ℃/min, and the temperature is kept for 5-6 min.
10. The method according to claim 1, wherein in step 2), the conditions of the mass spectrometer for thermal desorption-gas mass spectrometry detection are as follows:
electron ionization source: EI;
ionization voltage: 69-71 eV;
transmission line temperature: 220 to 240 ℃;
ion source temperature: 220 to 240 ℃;
quadrupole temperature: 145 to 155 ℃;
solvent retardation: 3-4 min;
detection mode: the total ion flow map of the full scan is qualitative and/or quantitative with a selected ion monitoring regime.
CN202211073099.9A 2022-09-02 2022-09-02 Method for detecting influence of different migration ways on inner lining paper barrier property Pending CN115326992A (en)

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CN103616360A (en) * 2013-12-05 2014-03-05 云南烟草科学研究院 Method for detecting specific migration volume of fluorescent whitening agent in paper
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CN112924595A (en) * 2021-01-27 2021-06-08 上海烟草集团有限责任公司 Method for detecting acrylic resin monomer migration volume in paper packaging material
CN113341018A (en) * 2021-06-08 2021-09-03 上海烟草集团有限责任公司 Method for measuring migration amount of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO (maximum power point tracking)
CN113504333A (en) * 2021-08-20 2021-10-15 上海烟草集团有限责任公司 Method for detecting organic matter migration amount in paper packaging material
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103616360A (en) * 2013-12-05 2014-03-05 云南烟草科学研究院 Method for detecting specific migration volume of fluorescent whitening agent in paper
CN104215732A (en) * 2014-09-26 2014-12-17 云南中烟工业有限责任公司 Method of taking Tenax as simulant to measure migration amount from paper and volatile and semi-volatile organic matter in paperboard by TD-GC/MS
CN112924595A (en) * 2021-01-27 2021-06-08 上海烟草集团有限责任公司 Method for detecting acrylic resin monomer migration volume in paper packaging material
CN113341018A (en) * 2021-06-08 2021-09-03 上海烟草集团有限责任公司 Method for measuring migration amount of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO (maximum power point tracking)
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