CN113341018B - Method for measuring migration quantity of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO - Google Patents

Method for measuring migration quantity of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO Download PDF

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CN113341018B
CN113341018B CN202110639265.6A CN202110639265A CN113341018B CN 113341018 B CN113341018 B CN 113341018B CN 202110639265 A CN202110639265 A CN 202110639265A CN 113341018 B CN113341018 B CN 113341018B
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printing paper
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CN113341018A (en
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虞桂君
吴秉宇
李登科
王先颖
沈世豪
崔体强
韩峰
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Shanghai Tobacco Group Co Ltd
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    • 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
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    • 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
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    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
    • 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
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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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
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Abstract

The invention provides a method for measuring migration quantity of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO, which comprises the following steps: and migrating components to be detected in the packaging printing paper sample into modified polyphenyl ether MPPO, carrying out oscillation mixing on the obtained modified polyphenyl ether migration sample, and then carrying out thermal desorption-gas chromatography-mass spectrometry on the obtained modified polyphenyl ether to-be-detected sample to determine migration amounts of 10 volatile and semi-volatile compounds in the packaging printing paper sample to the MPPO. The method for measuring the migration quantity of 10 volatile and semi-volatile compounds in the packaging printing paper to the MPPO has the advantages of simplicity in operation, high sensitivity, accurate measurement result, good repeatability, higher sensitivity to substances with higher boiling point and lower content, and remarkable advantages.

Description

Method for measuring migration quantity of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO
Technical Field
The invention belongs to the technical field of component analysis in packaging printing paper, relates to a method for measuring migration quantity of 10 volatile and semi-volatile compounds to MPPO in packaging printing paper, and in particular relates to a method for measuring specific migration quantity of 10 volatile and semi-volatile compounds to modified polyphenyl ether (MPPO) in packaging printing paper, wherein the specific migration quantity is composed of n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-methylphenol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate and 1, 6-hexanediol diacrylate
Background
The packaging printing paper may introduce some volatile and semi-volatile substances during the production and processing process, such as solvent residues in the base paper and the ink, peculiar smell substances and the like, and these substances may migrate to the packaging content during the production and storage process, causing quality safety hazards or affecting the quality of the content. Paper printing materials are often used for packaging dry foods, and when migration experiments are carried out on dry foods, (EU) No.10/2011, plastic materials and products to be contacted with foods, is proposed, and Res AP (2002) 1, technical document 2, guidelines on testing conditions and analytical methods of paper and paperboard materials and products to be contacted with foods, explicitly indicates that modified polyphenylene ether is used as a simulator. Modified polyphenylene oxide (MPPO), which is a porous polymer, is widely used for collecting volatile or semi-volatile substances in gases, liquids and solids.
European Union Standard EN 14338-2003, "conditions for determining migration of substances in paper and paperboard Using modified polyphenylene oxides as a mimetic", states that when migration experiments are conducted using MPPO as a dried food mimetic, the use of the mimetic and paper is 1dm 2 The paper or paperboard material of (2) corresponds to 4g of MPPO, and the suitability of the MPPO needs to be scientifically verified if the MPPO consumption is reduced in equal proportion. In most of the reported articles and patents, the requirement is not strictly complied with, the migration experiment is not carried out according to the required proportion, the dosage is reduced according to the same proportion, and the applicability is not verified. Thus, if a set of migration devices is selected, strict adherence to 1dm is observed 2 The migration experiment is carried out on the paper or paperboard material corresponding to the dosage of 4g MPPO, and the verification link can be omitted and the workload is reduced while the operation is standardized.
There are various pretreatment methods of MPPO, and there are solvent extraction method, headspace method, etc. commonly used. The solvent extraction method is more visual and has strong operability, but generally assists low-temperature rotary evaporation or nitrogen blowing to concentrate, and the loss of a target object is easy to cause in the period; the headspace method is simple to operate, but matrix correction agent is needed to be introduced during quantification, and the sensitivity of the headspace method is low for semi-volatile substances with slightly higher boiling points.
In recent years, research on migration of chemicals in paper packaging materials, such as antioxidants, plasticizers, specific aromatic amines, diisopropylnaphthalene, phthalates, preservatives, and the like, has been reported in the literature using MPPO as a mimetic. Volatile organic compounds such as methanol, ethanol, ethyl acetate, 1-methoxy-2-propanol, benzene compounds and the like are also included, but most of the compounds belong to volatile solvent residual substances with lower boiling points, and the residual amount of part of the compounds in paper is lower, even lower than the migration limit requirement, so that the migration amount test is unnecessary. Therefore, in consideration of practicality, in combination with actual residual conditions of volatile and semi-volatile compounds in the packaging printing paper and migration risk assessment, it is of great importance to establish a more practical detection method for migration amount of volatile and semi-volatile substances.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a method for measuring the migration amount of 10 volatile and semi-volatile compounds to MPPO in a packaging printing paper, which provides a practical and standardized measurement of the migration amount of 10 volatile and semi-volatile compounds (n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate, 1, 6-hexanediol diacrylate) in a packaging printing paper with simple pretreatment and high sensitivity by ATD-GC/MS technology.
To achieve the above and other related objects, the present invention provides a method for measuring the migration amount of 10 volatile and semi-volatile compounds to MPPO in a packaging printing paper, comprising: and (3) migrating components to be detected in the packaging printing paper sample into modified polyphenyl ether (MPPO), carrying out oscillation mixing on the obtained modified polyphenyl ether migration sample, and then carrying out thermal desorption-gas chromatography-mass spectrometry (ATD-GC/MS) measurement on the obtained modified polyphenyl ether to be detected sample to determine migration amounts of 10 volatile and semi-volatile compounds in the packaging printing paper sample to the MPPO.
Preferably, the migration of the component to be tested in the packaging printing paper sample to the modified polyphenylene oxide (MPPO) is performed in a migration device as shown in fig. 1, which is a device in patent No. ZL 201621312352.1. The device comprises bottom layer plate, intermediate level plate and top cap, and bottom is circular in bottom layer plate and the intermediate level plate, and the diameter is 113mm, can ensure the area of migration experiment paper sample. The device can be stacked and expanded by adopting any number of intermediate layer plates according to test requirements, and the inner space of each layer of plate is in a sealed and isolated state.
Preferably, when the component to be tested in the packaging printing paper sample migrates to the modified polyphenylene oxide (MPPO), the packaging printing paper sample is paved on the modified polyphenylene oxide (MPPO), and the modified polyphenylene oxide (MPPO) is added into the mixture of the mass g and the paving area dm of the packaging printing paper sample 2 The ratio is 3.5-4.5:1, preferably 4:1.
More preferably, the printed side of the wrapper sample is facing up.
More preferably, the modified polyphenylene oxide (MPPO) is heated to reflux with acetone before use, and then dried for purification.
Further preferably, the ratio of the added mass g of the modified polyphenylene ether (MPPO) to the added volume ml of acetone is 1:9-11, preferably 1:10.
Further preferably, the temperature of the heated reflux is 60-65 ℃, preferably 63 ℃; the heating reflux time is 5.5-6.5h, preferably 6h.
Preferably, the migration of the component to be tested in the packaging printing paper sample to the modified polyphenylene oxide (MPPO) is performed in an incubator.
Preferably, when the component to be tested in the packaging printing paper sample migrates to modified polyphenylene oxide (MPPO), the migration temperature is 35-45 ℃, preferably 40 ℃; the migration time is 9-11 days, preferably 10 days. The proper migration test temperature and migration time can be selected according to the actual package storage conditions or test requirements.
Preferably, the components to be tested in the packaging printing paper sample migrate to modified polyphenylene oxide (MPPO) and cool to room temperature. The room temperature is 20-30 ℃.
Preferably, the modified polyphenylene oxide (MPPO) has a particle size of 60 to 80 mesh.
The modified polyphenylene ether (MPPO), also known as Tenax TA, is a commercially available adsorbent conventionally used and is commercially available. Specifically, the modified polyphenylene ether (MPPO) is a modified polyphenylene ether (MPPO) purchased from the family of chromatography (Supelco).
The modified polyphenyl ether (MPPO) is evenly paved at the bottom of a bottom plate of the migration device, then the printing surface of the packaging printing paper sample is paved on the MPPO upwards, the migration device is sealed, the packaging printing paper sample is placed in an incubator with a certain temperature to migrate for a certain time, and the packaging printing paper sample is taken out after the packaging printing paper sample is ended.
Preferably, the blank test is performed when the component to be tested in the packaging printing paper sample migrates to modified polyphenylene oxide (MPPO). No wrapper paper sample was added to the blank.
Preferably, the modified polyphenylene ether migration sample is transferred to a glass sample bottle and sealed and then mixed with shaking.
Preferably, the shaking mixing is vortex shaking mixing, and the time of the shaking mixing is 0.1-1.0min, preferably 0.5min; the rotational speed of the shaking mixing is 1500-2500r/min, preferably 2000r/min. Ensure uniform mixing.
Preferably, the thermal desorption-gas chromatography-mass spectrometry (ATD-GC/MS) of the sample to be tested of the modified polyphenyl ether comprises the following steps:
1) Preparing an internal standard solution: providing an internal standard solution comprising benzyl acetate and a solvent;
2) Preparing a reference substance solution: providing a reference solution, wherein the reference solution comprises one or more reference substances selected from n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate or 1, 6-hexanediol diacrylate and a solvent;
3) And (3) measuring: filling a sample to be tested of modified polyphenyl ether into a thermal desorption tube, and adding a solvent and the internal standard solution in the step 1) to carry out thermal desorption (ATD); adding the internal standard solution in the step 1) into the reference substance solution in the step 2), and performing thermal desorption (ATD) in a thermal desorption tube; and respectively carrying out gas chromatography-mass spectrometry (GC/MS) measurement, comparing the retention time for qualitative determination, and adopting an internal standard curve method for quantitative determination to determine the contents of 10 volatile and semi-volatile compounds in the modified polyphenyl ether to-be-measured sample.
More preferably, in step 1) or 2), the solvent is methanol.
More preferably, in step 1), the internal standard solution is a methanol solution of benzyl acetate at a concentration of 5-15. Mu.g/mL, preferably 10. Mu.g/mL. The CAS numbers for benzyl acetate are shown in Table 1.
More preferably, in the step 2), the reference solution is obtained by adding one or more reference substances selected from n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate and 1, 6-hexanediol diacrylate into a solvent and gradually diluting.
More preferably, in the step 2), the content of n-butyl acrylate is 1-50 μg/mL, the content of isooctyl acetate is 4-200 μg/mL, the content of isooctyl acrylate is 1-50 μg/mL, the content of 2-ethylhexanol is 10-500 μg/mL, the content of diethylene glycol monoethyl ether is 10-500 μg/mL, the content of 2, 6-di-tert-butyl-p-cresol is 2-100 μg/mL, the content of 4-phenyl-1-cyclohexene is 0.4-20g/mL, the content of 1-phenyl-2-butanone is 4-200 μg/mL, the content of diethylene glycol butyl ether acetate is 1-50 μg/mL, and the content of 1, 6-hexanediol diacrylate is 2-100 μg/mL.
More preferably, in the step 3), the ratio of the sample injection mass mg of the sample to be detected of the modified polyphenyl ether, the sample injection volume muL of the solvent and the sample injection volume muL of the internal standard solution is 150-200:0.5-10:0.5-10; preferably 180:1:1.
Further preferably, the sample injection mass of the sample to be measured of the modified polyphenylene ether is 150-200mg (accurate to 0.1 mg), preferably 180mg (accurate to 0.1 mg).
Further preferably, the solvent is injected in a volume of 0.5 to 10. Mu.L, preferably 1. Mu.L.
Further preferably, the sample volume of the internal standard solution is 0.5-10. Mu.L, preferably 1. Mu.L.
More preferably, in the step 3), the ratio of the sample injection volume of the reference solution to the sample injection volume of the internal standard solution is 0.5-10:0.5-10, preferably 1:1.
Further preferably, the control solution has a sample volume of 0.5 to 10. Mu.L, preferably 1. Mu.L.
Further preferably, the sample volume of the internal standard solution is 0.5-10. Mu.L, preferably 1. Mu.L.
More preferably, in step 3), the conditions under which the solvent and the internal standard solution are introduced into the thermal desorption tube and/or the control solution and the internal standard solution are introduced into the thermal desorption tube are as follows: carrier gas: helium gas; the carrier gas flow mode is constant flow; the carrier gas flow rate is 80-120mL/min, preferably 100mL/min; the temperature of the sample inlet is 275-285 ℃, preferably 280 ℃; the furnace temperature is 35-45deg.C, preferably 40deg.C, and maintained for 0.5-1.5min, preferably 1min. Introduction was performed using an autosampler.
More preferably, in step 3), the thermal desorption tube is a glass hollow tube. The method is used for filling the sample to be tested of the modified polyphenyl ether, and aging is not needed before use.
More preferably, in step 3), the thermal desorption tube is a commercially available thermal desorption tube which is conventionally used. Specifically, for example, the thermal desorption tube is produced by Supelco, inc. of the family chromatography
Figure BDA0003107030220000052
TA 60/80 mesh (O.D.×L 1/4in.× 3 1/2 in) thermal desorption tube.
More preferably, in step 3), the thermal analysis tube is aged prior to use. The aging is performed by an aging instrument.
Further preferably, the aging conditions are: the carrier gas is helium; the carrier gas flow is 90-110mL/min, preferably 100mL/min; the aging temperature is 250-350deg.C, preferably 300 deg.C; the aging time is 15-25min, preferably 20min.
More preferably, in step 3), the measurement conditions of the thermal desorption (ATD) are: the desorption temperature is 260-280 ℃, preferably 270 ℃; the desorption time is 9-11min, preferably 10min; the cold trap temperature is 3-5 ℃, preferably 4 ℃ (trapping); the desorption temperature is 270-290 ℃, preferably 280 ℃; the temperature of the transmission line is 240-260 ℃, preferably 250 ℃; the valve temperature is 240-260 ℃, preferably 250 ℃; the inlet desorption flow is 35-45mL/min, preferably 40mL/min; the inlet split flow is 26-28mL/min, preferably 27mL/min; the flow rate of the outlet into the chromatographic column is 1-3mL/min, preferably 2mL/min; the outlet split flow is 9-11mL/min, preferably 10mL/min.
More preferably, in step 3), the measurement conditions of the gas chromatography are: the column was a DB-WAX capillary column [60m (length). Times.0.32 μm (inner diameter). Times.0.25 μm (film thickness) ]; the carrier gas is helium (the purity is more than or equal to 99.999 percent); temperature programming conditions: the initial temperature was 40℃for 5min, raised to 120℃at a rate of 4℃per min, and then raised to 200℃at a rate of 30℃per min, and maintained for 15min.
More preferably, in step 3), the determination conditions of the mass spectrum are: an electron ionization source (EI); ionization voltage 70eV; the temperature of the transmission line is 230 ℃; the ion source temperature is 230 ℃; the temperature of the four-stage rod is 150 ℃; delaying the solvent for 3min; detection mode: total ion flowsheet (TIC) characterization of the full scan, ion surveillance mode (SIM) quantification was selected.
Further preferably, the CAS numbers, retention times, and mass spectral parameters of the 10 volatile and semi-volatile compounds are set forth in table 1.
TABLE 1
Figure BDA0003107030220000051
Preferably, in step 3), the internal standard curve method includes the following steps:
a) Preparing a series of reference substance solutions with different concentrations according to the step 2), respectively adding the internal standard solutions prepared in the step 1), respectively performing ATD-GC/MS detection to obtain a linear relation between the chromatographic peak area ratio of 10 volatile and semi-volatile compounds/internal standards and the concentration ratio of the corresponding 10 volatile and semi-volatile compounds/internal standards, drawing a corresponding standard working curve, and calculating to obtain a regression equation of the standard working curve of the 10 volatile and semi-volatile compounds;
b) Adding a solvent into the modified polyphenyl ether to-be-detected sample and the internal standard solution prepared in the step 1), performing ATD-GC/MS detection, substituting the area ratio of the obtained 10 volatile and semi-volatile compounds to the chromatographic peak of the internal standard into a regression equation of the standard working curve of the corresponding 10 volatile and semi-volatile compounds in the step A), and calculating the concentration of the 10 volatile and semi-volatile compounds in the modified polyphenyl ether to-be-detected sample after subtracting the blank according to the known concentration of the internal standard solution.
More preferably, the standard working curve is plotted on the ordinate (Y-axis) against the area of the chromatographic peak of the 10 volatile and semi-volatile compounds against the internal standard, and the concentration ratio of the corresponding 10 volatile and semi-volatile compounds against the internal standard is plotted on the abscissa (X-axis).
Preferably, in the step 3), the contents of 10 volatile and semi-volatile compounds in the sample to be tested of the modified polyphenylene ether are calculated according to the formula (1) to obtain the specific migration amount of the 10 volatile and semi-volatile compounds in the packaging printing paper,
the formula (1) is:
Figure BDA0003107030220000061
wherein:
X i for a specific migration of target i (one of 10 volatile and semi-volatile compounds) in the packaging printing paper, micrograms per square meter (μg/m) 2 )；
c i For the concentration of target i (one of 10 volatile and semi-volatile compounds) in the sample to be tested of the modified polyphenylene ether, micrograms per milliliter (μg/mL);
v is the volume of solvent added in the thermal desorption tube, milliliters (mL);
m 1 g (g) is the total mass of the modified polyphenylene ether MPPO;
m 2 the mass of the sample to be detected of the modified polyphenyl ether filled in the thermal desorption tube is in grams (g);
s is the cutting area of the packaging printing paper sample, square meter (m 2 )。
The end result is packaging of volatile and semi-volatile compounds in printed paper per unit areaMigration amount of the substance (i.e., μg/m) 2 ) And (5) counting.
As described above, the method for measuring the migration amount of 10 volatile and semi-volatile compounds to MPPO in the packaging printing paper provided by the invention adopts thermal desorption-gas chromatography (ATD-GC/MS) to measure the migration amount of 10 volatile and semi-volatile compounds (n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate and 1, 6-hexanediol diacrylate) to modified polyphenyl ether (MPPO) in the packaging printing paper. Specifically, the method is a method for quantitatively measuring 10 volatile and semi-volatile compounds by taking MPPO as a simulant, carrying out migration experiments on packaging printing paper under certain migration experiment conditions, weighing MPPO to be measured with certain quality after the migration experiments are finished, filling the MPPO to be measured into a thermal desorption tube, and adopting an ATD-GC/MS method. Has the following beneficial effects:
(1) The determination method provided by the invention is based on thermal desorption-gas chromatography technology, and is used for quantitatively detecting and analyzing the specific migration quantity of 10 volatile and semi-volatile compounds in the packaging printing paper for the first time.
(2) According to the determination method provided by the invention, methanol is used as a solvent to prepare the standard working solution and the internal standard solution, so that the solubility of the target object and the internal standard object is good, the boiling point of the methanol is low, the interference on the detection result is small, the residual amount in an instrument is small, and the instrument is easy to clean.
(3) The determination method provided by the invention has the advantages that the thermal desorption method is directly operated, the enrichment effect on the target substance is realized, and the determination method also has higher sensitivity on substances with higher boiling points and lower contents, and has remarkable advantages.
(4) According to the determination method provided by the invention, thermal desorption is adopted as a pretreatment method, so that the pretreatment is simple, the operation is simple, the sensitivity is high, the practicability and the standardization are realized, the internal standard is introduced for quantification in the subsequent detection, and the determination result is accurate and the repeatability is good.
(5) The measurement method provided by the invention adopts a customized glass migration device, and strictly adheres to 1dm 2 Is a paper of (2)Or the paperboard material is subjected to migration experiments corresponding to the dosage of 4g of MPPO, meets the requirements of relevant standards at home and abroad, and omits a verification link.
(6) The method for measuring provided by the invention selects the target volatile semi-volatile compound from actual points of view, and the developed method has more practicability.
Drawings
Fig. 1 is a schematic structural diagram of a migration apparatus according to the present invention.
FIG. 2 shows a gas chromatogram of migration of 10 volatile and semi-volatile compounds to MPPO in a wrapper of the present invention, wherein 1 is n-butyl acrylate; 2 is isooctyl acetate; 3 is isooctyl acrylate; 4 is 2-ethylhexanol; 5 is diethylene glycol monoethyl ether; 6 is 4-phenyl-1-cyclohexene; 7 is 1-phenyl-2-butanone; 8 is diethylene glycol butyl ether acetate; 9 is 2, 6-di-tert-butyl-p-cresol; 10 is 1, 6-hexanediol diacrylate; IS benzyl acetate.
Reference numerals in fig. 1
1. Bottom plate
2. Middle layer plate
3. Top cover
Detailed Description
The invention is further illustrated below in connection with specific examples, which are to be understood as being illustrative of the invention and not limiting the scope of the invention.
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The reagents and instrumentation used in the following examples were as follows:
1. reagent(s)
N-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate, 1, 6-hexanediol diacrylate, benzyl acetate (analytical grade, national drug); methanol, acetone (chromatographic purity, carbofuran); modified polyphenylene oxide MPPO (60-80 mesh, chromatograph).
2. Instrument for measuring and controlling the intensity of light
Turbo matrix 350 thermal desorption apparatus (PerkinElmer); 7890B-5977A gas chromatograph-mass spectrometer (Agilent corporation); model 9600 thermal analysis tube aging apparatus (CDS Co.); a Multi-Tube vortex mixer oscillator (Talboys); incubator (MMM company); XP603S analytical balance (Metler Toledo Co.).
Example 1
1. Sample pretreatment
Weighing 4g of clean MPPO, uniformly spreading on the bottom of a bottom plate of a migration device, and cutting to 1dm 2 The printing surface of the packaging printing paper sample is flatly paved on the MPPO, the migration device is sealed, the packaging printing paper sample is placed in an incubator at 40 ℃ for migration for 240 hours, and after the packaging printing paper sample is finished, the migration device is taken out and cooled to room temperature. Blank tests without the addition of the wrapper paper samples were performed simultaneously. The clean MPPO has a particle size of 60-80 mesh, and can be purified by heating and refluxing at 63 ℃ for 6 hours.
And after the migration experiment is finished, taking out the modified polyphenyl ether migration sample from the migration device, transferring the modified polyphenyl ether migration sample into a glass sample bottle, sealing and carrying out vortex oscillation at the rotating speed of 2000r/min for 0.5min, and ensuring uniform mixing to obtain a modified polyphenyl ether sample to be detected.
2. Preparing an internal standard solution
Benzyl acetate was used as an internal standard, methanol was used as a solvent, and a methanol solution of benzyl acetate having a concentration of 10. Mu.g/mL was prepared as an internal standard solution.
3. Preparing reference substance solution
Methanol is used as a solvent, n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate and 1, 6-hexanediol diacrylate reference substances are added, and the mixture is diluted step by step to prepare reference substance solutions with different concentrations of 1-6 levels. The specific concentrations are shown in Table 2.
TABLE 2 (concentration unit: μg/mL)
Figure BDA0003107030220000091
4. Measurement
Determination of a reference substance solution: firstly, ageing the thermal analysis tube by adopting an ageing instrument, wherein the ageing conditions are as follows: the carrier gas is helium; the carrier gas flow rate is 100mL/min; the aging temperature is 300 ℃; the aging time was 20min. Then, 1. Mu.L of each level of reference substance solution and 1. Mu.L of internal standard solution are respectively heated and gasified by an automatic sampler of a gas chromatograph and introduced into a thermal desorption tube for thermal desorption. The introduction conditions are as follows: carrier gas: helium gas; the carrier gas flow mode is constant flow; the carrier gas flow rate is 100mL/min; the temperature of the sample inlet is 280 ℃; the furnace temperature is 40 ℃ and kept for 1min.
Measurement of modified polyphenylene ether to-be-measured sample: 180mg (accurate to 0.1 mg) of modified polyphenyl ether sample to be detected is accurately weighed, filled into a glass thermal desorption tube, and 1 mu L of methanol and 1 mu L of internal standard solution are respectively heated and gasified by an automatic sampler of a gas chromatograph and introduced into the thermal desorption sample tube for thermal desorption. The introduction conditions were as above.
The measurement conditions of the thermal desorption are as follows: the desorption temperature is 270 ℃; the desorption time is 10min; the cold trap temperature is 4 ℃ (trapping); the desorption temperature is 280 ℃; the temperature of the transmission line is 250 ℃; the valve temperature was 250 ℃; the inlet desorption flow is 40mL/min; the inlet split flow is 27mL/min; the flow rate of the outlet into the chromatographic column is 2mL/min; the outlet split flow was 10mL/min. And then respectively carrying out gas chromatography-mass spectrometry (GC/MS) measurement, comparing the retention time for qualitative determination, and adopting an internal standard curve method for quantitative determination to determine the contents of 10 volatile and semi-volatile compounds in the modified polyphenyl ether to-be-measured sample.
Wherein, the measurement conditions of the gas chromatograph are as follows: the column was a DB-WAX capillary column [60m (length). Times.0.32 μm (inner diameter). Times.0.25 μm (film thickness) ]; the carrier gas is helium (the purity is more than or equal to 99.999 percent); temperature programming conditions: the initial temperature was 40℃for 5min, raised to 120℃at a rate of 4℃per min, and then raised to 200℃at a rate of 30℃per min, and maintained for 15min.
The measurement conditions of the mass spectrum are as follows: an electron ionization source (EI); ionization voltage 70eV; the temperature of the transmission line is 230 ℃; the ion source temperature is 230 ℃; the temperature of the four-stage rod is 150 ℃; delaying the solvent for 3min; detection mode: total ion flowsheet (TIC) characterization of the full scan, ion surveillance mode (SIM) quantification was selected.
Specific data for retention times and mass spectral parameters for 10 volatile and semi-volatile compounds are shown in table 1, fig. 2. Blank tests were performed synchronously.
Finally, the contents of 10 volatile and semi-volatile compounds in the sample to be tested of the modified polyphenyl ether are calculated according to a formula (1), and the specific migration quantity of the 10 volatile and semi-volatile compounds in the packaging printing paper is obtained, wherein the formula (1) is as follows:
Figure BDA0003107030220000101
wherein: x is X i For a specific migration of target i (one of 10 volatile and semi-volatile compounds) in the packaging printing paper, micrograms per square meter (μg/m) 2 )；c i For the concentration of target i (one of 10 volatile and semi-volatile compounds) in the sample to be tested of the modified polyphenylene ether, micrograms per milliliter (μg/mL); v is the volume of solvent added in the thermal desorption tube, milliliters (mL); m is m 1 G (g) is the total mass of the modified polyphenylene ether MPPO; m is m 2 The mass of the sample to be detected of the modified polyphenyl ether filled in the thermal desorption tube is in grams (g); s is the cutting area of the packaging printing paper sample, square meter (m 2 )。
Example 2
A series of control solutions of different concentrations were prepared as in step 3 of example 1, measured as in step 4 of example 1, and then standard working curves were plotted with the area ratio of the chromatographic peak of the 10 volatile and semi-volatile compounds to the internal standard on the ordinate (Y-axis) and the corresponding concentration ratio of the 10 volatile and semi-volatile compounds to the internal standard on the abscissa (X-axis). Regression equations for 10 volatile and semi-volatile compounds and their correlation coefficients were obtained as shown in table 3. From Table 3, standard working curves for 10 volatile and semi-volatile compounds are knownLinear correlation coefficient R of line 2 > 0.99, the linearity is good.
TABLE 3 Table 3
Figure BDA0003107030220000102
The control solution with the lowest concentration is subjected to 10 times of parallel detection analysis, the concentration corresponding to 3 times of standard deviation is taken as a detection limit of the method, 10 times of standard deviation is taken as a quantitative limit of the method, and specific results are shown in table 4. As is clear from Table 4, the detection limit and the quantitative limit were low, which indicates that the sensitivity of the method was good.
The recovery rate and repeatability of the method were verified by using the modified polyphenylene ether to-be-measured sample prepared in step 1 of example 1 as a sample, and the specific results are shown in table 4. As can be seen from Table 4, the daily and daytime repeatability of the 10 volatile and semi-volatile compounds were all less than 5%, indicating good process repeatability; according to the actual content of the target in the sample to be detected of the modified polyphenyl ether, the target is marked by 0.5 times, 1 time and 2 times respectively, and the recovery rate of 10 target is 83.4-109.7%, which indicates that the recovery rate of the method is high.
TABLE 4 Table 4
Figure BDA0003107030220000111
Example 3
4 homemade positive paper samples (numbered 1# to 4 #) were selected, and a migration experiment and quantitative detection of the specific migration amounts of 10 targets in the paper samples were performed as in example 1, and the results are shown in table 5. As can be seen from Table 5, the method of the present application can accurately determine the specific migration amounts of 10 targets in a paper sample.
Table 5 results of detection of specific migration amounts of 10 target substances in paper samples (unit: μg/m) 2 )
Figure BDA0003107030220000112
In summary, the method for measuring the migration quantity of 10 volatile and semi-volatile compounds to MPPO in the packaging printing paper provided by the invention has the advantages of simplicity in operation, high sensitivity, accurate measurement result, good repeatability, higher sensitivity to substances with higher boiling points and lower content, and remarkable advantages. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (8)

1. A method for determining the migration of 10 volatile and semi-volatile compounds to MPPO in a packaging printing paper, comprising: migrating components to be detected in a packaging printing paper sample into modified polyphenyl ether, carrying out oscillation mixing on the obtained modified polyphenyl ether migration sample, and then carrying out thermal desorption-gas chromatography-mass spectrometry on the obtained modified polyphenyl ether to-be-detected sample to determine migration amounts of 10 volatile and semi-volatile compounds in the packaging printing paper sample to MPPO;
10 volatile and semi-volatile compounds in the printing paper are n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate and 1, 6-hexanediol diacrylate;
the thermal desorption-gas chromatography-mass spectrometry determination of the modified polyphenyl ether sample to be detected comprises the following steps:
1) Preparing an internal standard solution: providing an internal standard solution comprising benzyl acetate and a solvent;
2) Preparing a reference substance solution: providing a reference solution, wherein the reference solution comprises n-butyl acrylate, isooctyl acetate, isooctyl acrylate, 2-ethylhexanol, diethylene glycol monoethyl ether, 2, 6-di-tert-butyl p-cresol, 4-phenyl-1-cyclohexene, 1-phenyl-2-butanone, diethylene glycol butyl ether acetate, a 1, 6-hexanediol diacrylate reference and a solvent;
3) And (3) measuring: filling a sample to be tested of modified polyphenyl ether into a thermal desorption tube, and adding a solvent and the internal standard solution in the step 1) to carry out thermal desorption; adding the internal standard solution in the step 1) into the reference substance solution in the step 2), and performing thermal desorption in a thermal desorption tube; respectively carrying out gas chromatography-mass spectrometry, comparing the retention time for qualitative determination, and adopting an internal standard curve method for quantitative determination to determine the contents of 10 volatile and semi-volatile compounds in the modified polyphenyl ether to-be-detected sample;
in the step 1) or 2), the solvent is methanol;
in step 3), the measurement conditions of the gas chromatograph are: the chromatographic column is DB-WAX capillary chromatographic column, 60m length is multiplied by 0.32 mu m inner diameter is multiplied by 0.25 mu m film thickness; the carrier gas is helium, and the purity is more than or equal to 99.999%; temperature programming conditions: the initial temperature was 40℃for 5min, raised to 120℃at a rate of 4℃per min, and then raised to 200℃at a rate of 30℃per min, and maintained for 15min.
2. A method of determining the amount of migration of 10 volatile and semi-volatile compounds to MPPO in a packaging printing paper according to claim 1, comprising any one or more of the following conditions:
a) When the components to be detected in the packaging printing paper sample migrate to the modified polyphenyl ether, the packaging printing paper sample is flatly paved on the modified polyphenyl ether, the ratio of the adding mass of the modified polyphenyl ether to the flatly paved area of the packaging printing paper sample is 3.5-4.5:1,
g/dm 2 ；
b) When components to be detected in the packaging printing paper sample migrate to the modified polyphenyl ether, the migration temperature is 35-45 ℃ and the migration time is 9-11 days;
c) The vibration mixing is vortex vibration mixing, and the time of the vibration mixing is 0.1-1.0min; the rotation speed of the oscillating mixture is 1500-2500r/min.
3. The method for measuring the migration of 10 volatile and semi-volatile compounds to MPPO in a packaging paper according to claim 1 wherein in step 1), said internal standard solution is a methanol solution of benzyl acetate having a concentration of 5-15 μg/mL.
4. The method for determining the amount of migration of 10 volatile and semi-volatile compounds to MPPO in a packaging paper according to claim 1, wherein in step 3), the conditions for introducing the solvent and the internal standard solution into the thermal desorption tube and/or for introducing the reference solution and the internal standard solution into the thermal desorption tube are as follows: carrier gas: helium gas; the carrier gas flow mode is constant flow; the flow rate of the carrier gas is 80-120mL/min; the temperature of the sample inlet is 275-285 ℃; the furnace temperature is 35-45 ℃ and kept for 0.5-1.5min.
5. A method for determining the amount of migration of 10 volatile and semi-volatile compounds to MPPO in a packaging sheet according to claim 1 wherein in step 3) said thermal analysis tube is aged prior to use; the aging conditions are as follows: the carrier gas is helium; the flow rate of the carrier gas is 90-110mL/min; the aging temperature is 250-350 ℃; the aging time is 15-25min.
6. The method for measuring the migration amount of 10 volatile and semi-volatile compounds to MPPO in a packaging printing paper according to claim 1, wherein in step 3), the measurement conditions of thermal desorption are: the desorption temperature is 260-280 ℃;
the desorption time is 9-11min; the temperature of the cold trap is 3-5 ℃; the desorption temperature is 270-290 ℃; the temperature of the transmission line is 240-260 ℃; the valve temperature is 240-260 ℃; the inlet desorption flow is 35-45mL/min; the inlet split flow is 26-28mL/min; the flow rate of the outlet into the chromatographic column is 1-3mL/min; the flow rate of the outlet split flow is 9-11mL/min.
7. The method for measuring the migration of 10 volatile and semi-volatile compounds to MPPO in a packaging printing paper according to claim 1, wherein in step 3), the mass spectrum is measured under the following conditions: an electron ionization source EI; ionization voltage 70eV; the temperature of the transmission line is 230 ℃; the ion source temperature is 230 ℃; the temperature of the four-stage rod is 150 ℃; delaying the solvent for 3min; detection mode: total ion flow map TIC qualitative of full scan, ion monitoring mode SIM quantification was selected.
8. The method for measuring the migration amount of 10 volatile and semi-volatile compounds to MPPO in a packaging printing paper according to claim 1, wherein in step 3), the contents of 10 volatile and semi-volatile compounds in the sample to be measured of the modified polyphenylene ether are calculated according to formula (1) to obtain the specific migration amount of 10 volatile and semi-volatile compounds in the packaging printing paper,
the formula (1) is:
Figure FDA0004122009730000021
wherein:
X i for a specific migration of the object i in the packaging printing paper, μg/m 2 ；
c i The concentration of a target object i in a sample to be detected of the modified polyphenyl ether is mug/mL;
v is the volume of solvent added into the thermal desorption tube and mL;
m 1 g is the total mass of the modified polyphenyl ether;
m 2 g, the mass of a sample to be detected of the modified polyphenyl ether filled in the thermal desorption tube;
s is the cutting area of the packaging printing paper sample, m 2 。
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