CN114487163A - Method for measuring neopentyl glycol migration amount in food contact material and product - Google Patents
Method for measuring neopentyl glycol migration amount in food contact material and product Download PDFInfo
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Abstract
The application provides a method for determining the neopentyl glycol migration amount in food contact materials and products, which comprises the steps of sampling; preprocessing and detecting the migration amount of neopentyl glycol in the preprocessed sample solution; the method comprises the following steps of (1) detecting the migration amount of a target substance in a pretreated sample solution, wherein the target substance in the pretreated sample solution is neopentyl glycol phenylboronate, and the step of detecting the migration amount of the target substance in the pretreated sample solution comprises the following steps: and determining the content of neopentyl glycol phenylboronate by a GC-MS analyzer, and determining the migration amount of neopentyl glycol according to the content of neopentyl glycol phenylboronate. The migration amount of the neopentyl glycol is calculated through the content of the neopentyl glycol phenylboronate, the requirement for determining the food additive in the food contact container can be met, the detection method is simple and efficient, the detection limit is low, the quantification is accurate, and the related detection requirements can be met.
Description
Technical Field
The application relates to the technical field of food detection, in particular to a method for measuring neopentyl glycol migration amount in food contact materials and products.
Background
Neopentyl glycol is an important chemical raw material, contains 2 symmetrical primary hydroxyl groups in the molecular structure, is easy to rapidly participate in various chemical reactions such as esterification, condensation, oxidation and the like, and is widely applied to the fields of chemical industry, textiles, medicines, coatings, pesticides, automobiles, plastics, petroleum and the like. Coating resins based on neopentyl glycol are essential components for the preparation of powder coatings and high-solids coatings. Neopentyl glycol can also be used as a plasticizer for producing unsaturated polyester resins, oil-free alkyd resins, polyurethane foams and elastomers, has water resistance, chemical resistance and weather resistance, and is an important industrial additive and stabilizer.
Neopentyl glycol is a low-toxicity substance, but a large amount of neopentyl glycol is taken into a human body to stimulate central nerves, so that a series of serious symptoms are easily caused, and even death can be caused in serious cases. Therefore, in the case of food contact materials, there are clear limit requirements for neopentyl glycol to be used as an additive for food contact materials and products, and for neopentyl glycol to remain in plastic resins for food contact. GB 9685-2016 specifies that the specific migration of neopentyl glycol as an additive in food-contact plastics, coatings and adhesives must not exceed 0.05 mg/kg; GB 4806.6-2016 specifies that the specific migration of neopentyl glycol in PUR and PTT plastics for food contact should not exceed 0.05 mg/kg.
Liuyi Yong et al, quantitative analysis [ J ] of neopentyl glycol in a water-based multi-component system, chemical research and application, 2010,22(03): 339-. At present, the quantitative analysis of neopentyl glycol is mostly carried out by adopting an acetic anhydride-sodium acetate chemical method for determination, and the method aims at the detection of neopentyl glycol in a non-water-based system, is complex to operate and is not suitable for the requirement of determination of food additives in food contact containers.
Disclosure of Invention
In view of the problems described, the present application has been developed to provide a method for determining the amount of neopentyl glycol migration in food contact materials and articles that overcomes or at least partially solves the problems described above, comprising:
a method for determining the amount of neopentyl glycol migration in food contact materials and articles comprising the steps of: sampling; pretreating and detecting the migration quantity of a target object in the pretreated sample solution;
wherein the pretreatment step comprises:
when the sample is a water-based simulant test solution, mixing the sample with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated;
or;
when the sample is an oil-based simulant test solution, mixing the sample with a second extracting agent, carrying out oscillation treatment for a second designated time, and after standing and layering, obtaining a lower-layer phase solution as an extraction liquid; mixing the extract with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernate, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated;
the method comprises the following steps of (1) detecting the migration amount of a target substance in a pretreated sample solution, wherein the target substance in the pretreated sample solution is neopentyl glycol phenylboronate, and the step of detecting the migration amount of the target substance in the pretreated sample solution comprises the following steps:
and determining the content of neopentyl glycol phenylboronate by a GC-MS analyzer, and determining the migration amount of neopentyl glycol according to the content of neopentyl glycol phenylboronate.
Further, the method also comprises the following steps:
the step of measuring the content of neopentyl glycol phenylboronate by a GC-MS analyzer to calculate the content of neopentyl glycol comprises the following chromatographic conditions:
after the sample solution to be pretreated is placed into a chromatographic column, maintaining the temperature of the chromatographic column at 60 ℃ for 2min, and recording the chromatographic change in real time;
raising the temperature of the chromatographic column to 180 ℃ at a temperature rise rate of 15 ℃/min, and recording the chromatographic change in real time;
raising the temperature of the chromatographic column to 300 ℃ at a temperature raising speed of 30 ℃/min, maintaining the temperature of the chromatographic column at 300 ℃ for 1min, and recording the chromatographic change in real time.
Further, the step of calculating the content of neopentyl glycol by measuring the content of neopentyl glycol phenylboronate with a GC-MS analyzer comprises the following mass spectrum conditions:
mass spectrum interface temperature: 300 ℃;
ion source temperature: 230 ℃;
quadrupole temperature: 150 ℃;
mass spectrometry scan mode: selecting an ion scan and a full scan;
quantification of neopentyl glycol phenylboronate: m/z 105; and (3) qualitative ion: m/z 190, m/z56, m/z 77.
Further, the first extracting agent is at least one of toluene, isooctane, n-hexane, n-heptane and ethyl acetate; the second extracting agent is at least one of toluene, isooctane, n-hexane, n-heptane and ethyl acetate.
Further, the volume ratio of the sample to the first extractant is 2 mL: 1 mL.
Further, the volume ratio of the sample to the second extractant is 1 mL: 1 mL.
Further, the volume ratio of the sample to the derivatizing agent is 10 mL: 1 mL.
Further, the mass ratio of the phenylboronic acid to the sodium chloride solid to the first extractant is 1 mL: 2 g: 5 mL.
Further, the water-based food simulant test solutions are at least one of 4% acetic acid, 10% ethanol and 50% ethanol, respectively; the oil-based food simulant test solution is olive oil.
Further, the first specified time is 30 min; the second designated time is 2 min.
The application has the following advantages:
in the embodiments of the present application, the sampling is performed; pretreating and detecting the migration quantity of a target object in the pretreated sample solution; wherein the pretreatment step comprises: when the sample is a water-based simulant test solution, mixing the sample with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated; or; when the sample is an oil-based simulant test solution, mixing the sample with a second extracting agent, carrying out oscillation treatment for a second designated time, and after standing and layering, obtaining a lower-layer phase solution as an extraction liquid; mixing the extract with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated; the method comprises the following steps of (1) detecting the migration amount of a target substance in a pretreated sample solution, wherein the target substance in the pretreated sample solution is neopentyl glycol phenylboronate, and the step of detecting the migration amount of the target substance in the pretreated sample solution comprises the following steps: and determining the content of neopentyl glycol phenylboronate by a GC-MS analyzer, and determining the migration amount of neopentyl glycol according to the content of neopentyl glycol phenylboronate. The migration amount of the neopentyl glycol is calculated through the content of the neopentyl glycol phenylboronate, the requirement for determining the food additive in the food contact container can be met, the detection method is simple and efficient, the detection limit is low, the quantification is accurate, and the related detection requirements can be met.
Drawings
In order to more clearly illustrate the technical solutions of the present application, the drawings required to be used in the description of the present application will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings may be obtained according to these drawings without inventive labor.
FIG. 1 is a flow chart illustrating the steps of a method for determining the migration of neopentyl glycol from a food contact material and an article according to one embodiment of the present application;
FIG. 2 is a schematic diagram of a neopentyl glycol derivatization reaction provided in an example of the present application;
FIG. 3 is a chromatogram of a neopentyl glycol derivatization product provided in an example of the present application;
FIG. 4 is a characteristic ion mass spectrum of a derivatized neopentyl glycol product provided in an example of the present application.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the descriptions related to "first", "second", etc. in the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the respective embodiments may be combined with each other, but must be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
Referring to fig. 1, in an embodiment of the present invention, the present invention provides a method for detecting migration amounts of ethylenediamine and hexamethylenediamine in food contact materials and products, including: s1, sampling; s2, preprocessing and S3, detecting the migration amount of neopentyl glycol in the preprocessed sample solution;
wherein the pretreatment step comprises:
s21, when the sample is a water-based simulant test solution, mixing the sample with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated;
or;
s22, or; when the sample is an oil-based simulant test solution, mixing the sample with a second extracting agent, carrying out oscillation treatment for a second designated time, and after standing and layering, obtaining a lower-layer phase solution as an extraction liquid; mixing the extract with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated;
the method comprises the following steps of (1) detecting the migration amount of a target substance in a pretreated sample solution, wherein the target substance in the pretreated sample solution is neopentyl glycol phenylboronate, and the step of detecting the migration amount of the target substance in the pretreated sample solution comprises the following steps:
and S31, determining the content of neopentyl glycol phenylborate ester by a GC-MS analyzer, and determining the migration amount of neopentyl glycol according to the content of neopentyl glycol phenylborate ester.
In the embodiments of the present application, the sampling is performed; pretreating and detecting the migration quantity of a target object in the pretreated sample solution; wherein the pretreatment step comprises: when the sample is a water-based simulant test solution, mixing the sample with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated; or; when the sample is an oil-based simulant test solution, mixing the sample with a second extracting agent, carrying out oscillation treatment for a second designated time, and after standing and layering, obtaining a lower-layer phase solution as an extraction liquid; mixing the extract with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated; the method comprises the following steps of (1) detecting the migration amount of a target substance in a pretreated sample solution, wherein the target substance in the pretreated sample solution is neopentyl glycol phenylboronate, and the step of detecting the migration amount of the target substance in the pretreated sample solution comprises the following steps: and determining the content of neopentyl glycol phenylboronate by a GC-MS analyzer, and determining the migration amount of neopentyl glycol according to the content of neopentyl glycol phenylboronate. The migration amount of the neopentyl glycol is calculated through the content of the neopentyl glycol phenylboronate, the requirement for determining the food additive in the food contact container can be met, the detection method is simple and efficient, the detection limit is low, the quantification is accurate, and the related detection requirements can be met.
Next, the method for measuring the migration amount of neopentyl glycol in the food contact material and the article in the present exemplary embodiment will be further described.
As shown in step S1, sampling is generally one of the important steps of extracting a small amount of target substance from a target object for detection, and has one of the effective ways to obtain various data from the target object for testing without affecting the main properties of the target object, the extraction amount of the target object is sufficient for 3-5 times of testing, the process of selecting a sampling area of the target object during sampling is required to be random, and subjective selection cannot be mixed in the selection process, in the embodiment of the present invention, when the sampling weight is generally 5g-15g, preferably 10 g; the volume of the sample taken is generally 5mL to 15mL, preferably 10 mL.
As shown in step S2, the pretreatment step is generally a step for the purpose of impurity removal and purification before performing an effective process on the target object, and in some special experiments, the pretreatment step also includes the purpose of changing material properties, and in the embodiment of the present invention, the pretreatment step is preferably the steps S21-S23.
Detecting the migration amount of neopentyl glycol in the pretreated sample solution in the step S3, which is generally a step of performing a specified experiment or detection on the target object after the step S1-S2, and generally obtaining direct data or indirect data, wherein the direct data is data of which the data is directly a detected target value or result; the indirect data is data of a target value or result obtained only after corresponding calculation, replacement or comparison, the detection result generally has a deviation value according to the deviation of detection equipment, environment, preprocessing steps and auxiliary products, and after the difference between the preprocessing step and the auxiliary products is used for formulating a detection standard, the error amplitude caused by the preprocessing step and the auxiliary products can be correspondingly and effectively avoided.
When the sample is the water-based simulant test solution, mixing the sample with phenylboronic acid to obtain a first solution as described in step S21; adding sodium chloride solid and a first extracting agent into a first solution, carrying out oscillation treatment for a first designated time, standing for layering, taking a supernatant, mixing the supernatant with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated, wherein in the process of carrying out the step S21, the sample and the phenylboronic acid are required to be fully mixed, wherein the sample and the phenylboronic acid are added into a 50mL screw-top test tube with a cover, and therefore after the two are added into the same container, the sample and the phenylboronic acid are required to be covered by the cover for shaking up or stirring treatment. In the present examples, the amount of phenylboronic acid used is generally 0.5 to 3mL, preferably 1 mL.
In the embodiment of the present application, the derivatization reaction of neopentyl glycol converts neopentyl glycol into corresponding neopentyl glycol phenylborate ester through phenylboronic acid, and then detects the compound obtained by the conversion, so as to obtain a good qualitative and quantitative detection result, wherein the reaction principle of neopentyl glycol and phenylboronic acid is shown in fig. 2.
In the embodiment of the application, a food simulant migration test is performed on food contact materials and products according to national mandatory food safety standards GB5009.156-2016 and GB 31604.1-2015 to obtain a water-based food simulant test solution (with a volume fraction of 4% acetic acid, a volume fraction of 10% ethanol, and a volume fraction of 50% ethanol), the volume fraction of 4% acetic acid, the volume fraction of 10% ethanol, and the volume fraction of 50% ethanol after the migration test are respectively mixed with phenylboronic acid to obtain a first solution, namely a neopentyl glycol phenylboronate solution, during the implementation of the step S21, sodium chloride solids and a first extractant are added into the first solution to be fully mixed, and therefore, after the two are added into the same container, shaking or stirring treatment is required. In the embodiment of the present invention, the first extracting agent may include a plurality of different reagents, or may be a single kind of reagent, in the embodiment of the present invention, the first extracting agent is at least one of toluene, isooctane, n-hexane, n-heptane, and ethyl acetate, preferably n-hexane, the first solution, the sodium chloride solid and the first extracting agent are mixed to such an extent that the sodium chloride solid is completely dissolved in the first solvent and the first extracting agent, and the mixture is contacted with each other in the same reactor, and after the first solution is mixed with the sodium chloride solid and the first extracting agent, the mixed solution is subjected to a reciprocating oscillation process, wherein a first specified time lasting in the reciprocating oscillation process is generally 20 to 50min, preferably 30 min; wherein, the dosage of the sodium chloride solid is generally 1 to 3g, preferably 2 g; the amount of the first extractant used is generally 3 to 7mL, preferably 5 mL.
After standing and layering, mixing the supernatant with a dehydrating agent and dehydrating to obtain a sample solution to be pretreated, collecting the sample solution into a sample injection vial, standing the mixture of the first solution, the sodium chloride solid and the first extracting agent after reciprocating oscillation, and mixing the supernatant of the mixture with the dehydrating agent after complete layering; wherein the dosage of the supernatant is generally 0.5-2mL, preferably 1 mL; wherein, the dehydrating agent is preferably anhydrous sodium sulfate, and the dosage of the dehydrating agent is generally 0.2 to 1g, preferably 0.5 g.
When the sample is the oil-based simulant test solution, mixing the sample with a second extracting agent, performing oscillation treatment for a second designated time, and after standing and layering, obtaining a lower-layer phase liquid as an extraction liquid; mixing the extract with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated.
In the present example, the sample and the second extractant need to be added to the separatory funnel and sufficiently mixed, and therefore, after both are added to the same vessel, shaking or stirring treatment needs to be performed. And then adding deionized water into the separating funnel for carrying out oscillating extraction for a second designated time, and standing for layering. The second extraction agent may include a plurality of different reagents, and may also be a single kind of reagent, and in the embodiment of the present invention, the second extraction agent is at least one of toluene, isooctane, n-hexane, n-heptane and ethyl acetate, and preferably n-heptane; wherein the second designated time is generally 1-3min, preferably 2 min.
After the extraction and purification are carried out by adopting the second extractant, the lower-layer water phase part can be repeatedly extracted by using deionized water again, the two extraction solutions are combined, finally, most neopentyl glycol in the oil-based food sample solution is extracted into the water phase, and finally, the deionized water is used for fixing the volume of the extraction solution to 10 mL.
Mixing the extract with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first designated time, standing for layering, taking a supernatant, mixing the supernatant with a dehydrating agent, dehydrating, carrying out a food simulant migration test on food contact materials and products according to national mandatory food safety standards GB5009.156-2016 and GB 31604.1-2015, and obtaining an oil-based food simulant test solution (olive oil), wherein the step of obtaining the sample solution to be pretreated is the same as the step S21, and therefore, the steps are not repeated.
In this example, the volume ratio of the sample to the first extractant is 2 mL: 1 mL.
In this example, the volume ratio of the sample to the second extractant was 1 g: 1 mL.
In this example, the volume ratio of the sample to the derivatizing reagent was 10 mL: 1 mL.
In this example, the volume ratio of the phenylboronic acid, the sodium chloride solid, and the first extractant is 1 mL: 2 g: 5 mL.
In this embodiment, the water-based food simulant test solutions are at least one of 4% acetic acid, 10% ethanol, and 50% ethanol, respectively; the oil-based food simulant test solution is olive oil.
As stated in step S31, the target substance in the pretreated sample solution is neopentyl glycol phenylboronate, and the step of detecting the migration amount of the target substance in the pretreated sample solution includes:
and determining the content of neopentyl glycol phenylboronate by a GC-MS analyzer, and determining the migration amount of neopentyl glycol according to the content of neopentyl glycol phenylboronate.
Wherein, the use condition of the GC-MS analyzer in the detection process is preferably as follows in the embodiment of the invention: instrument type: GC-MS (Agilent 7890B-5977B);
a chromatographic column: DB-5MS (30m 0.25 μm film thickness x 0.25mm internal diameter);
carrier gas type: helium gas;
carrier gas flow rate: 1.2mL/min, constant current mode;
sample introduction volume: 1.0 μ L;
the split ratio is as follows: 10: 1;
sample inlet temperature: at 250 ℃ to obtain a mixture.
Temperature rising procedure: after the sample solution to be pretreated is placed into a chromatographic column, maintaining the temperature of the chromatographic column at 60 ℃ for 2min, and recording the chromatographic change in real time;
raising the temperature of the chromatographic column to 180 ℃ at a temperature rise rate of 15 ℃/min, and recording the chromatographic change in real time;
raising the temperature of the chromatographic column to 300 ℃ at a temperature raising speed of 30 ℃/min, maintaining the temperature of the chromatographic column at 300 ℃ for 1min, and recording the chromatographic change in real time.
Retention time, quantitative ions and target characteristic ions are shown in table one:
watch 1
In one embodiment, the step of performing qualitative analysis of neopentyl glycol phenylboronate using a GC-MS analyzer comprises:
determining a sample according to the use condition of the GC-MS analyzer;
and (3) measuring the pretreated sample solution under the same experimental conditions, and judging that the sample contains the target compound if the retention time of the detected chromatographic peak is consistent with that of the standard substance, and the mass spectrum of the sample after background subtraction is obtained, so that the characteristic ions of the target compound all appear, and the abundance ratio of the characteristic ions is consistent with that of the standard substance. Specifically, qualitative requirements are shown in table 2.
Watch two
In one embodiment, the step of quantitatively analyzing neopentyl glycol phenylboronate using a GC-MS analyzer comprises:
1) preparing a neopentyl glycol standard substance into a standard stock solution with the concentration of 1000mg/L by using absolute ethyl alcohol;
2) preparation of a water-based simulant standard working solution: neopentyl glycol standard stock solutions were diluted with water-based simulant (water, 4% acetic acid, 50% ethanol) solutions to 0.05, 0.10, 0.25, 1.00, 5.00mg/L standard working solutions (each test tube contained only one simulant);
3) preparing an oil-based simulant standard working solution: diluting neopentyl glycol standard stock solution with oil-based simulant (olive oil) test solution to standard working solution of 0.05, 0.10, 0.25, 1.00, 5.00mg/kg (each test tube contains only one simulant);
4) the water-based simulator standard substance test solutions are respectively 0.10, 0.20, 0.50, 2.00 and 10.00 mg/L; pretreating the water-based analogue standard working solution according to the step S21 to obtain a sample solution to be pretreated for GC-MS analysis;
5) the oil-based (olive oil) simulant standard substance test solutions are respectively 0.10, 0.20, 0.50, 2.00 and 10.00 mg/L; and (4) pretreating the oil-based simulant standard working solution according to the step S22 to obtain a sample solution to be pretreated for GC-MS analysis.
6) At least 5 concentration points of the calibration curve are respectively taken, and standard substance test solution with proper concentration and the sample are respectively subjected to instrumental analysis under the same conditions. And then, taking the peak area corresponding to the concentration of the standard substance test solution as a calibration curve to calculate a regression equation and a correlation coefficient. Then, the content of neopentyl glycol is calculated according to the content of neopentyl glycol phenylboronate, and the calculation formula is as follows:
in the formula: cNPGThe mass concentration of neopentyl glycol in the food simulant is in mg/kg; cCThe concentration of neopentyl glycol phenylborate ester read on the calibration curve is in mg/L; v is the final effective volume of the extraction solvent, and the unit is mL; m is the weight of the food simulant used for the determination, in g; DF is the dilution factor.
Referring to FIGS. 3-4, in one embodiment, a food simulant neopentyl glycol is subjected to a spiking test;
1) the migration test is carried out according to the expected application and use conditions of the sample to be tested and according to the migration test method and test conditions of food contact materials and products specified by national mandatory standards for food safety GB5009.156 and GB 31604.1. Cutting the sample to a proper area according to the area-volume ratio of 6dm2The migration test was performed using 4% acetic acid, 10% ethanol, 50% ethanol and olive oil as food simulants, respectively. Migration test conditions were determined according to the intended use and conditions of use of the sample as: the first step is carried out as follows "the expected most extreme contact temperature is 100 DEG C<T is less than or equal to 121 ℃, and the expected most extreme contact time T is less than or equal to 0.5h, namely 'the grease simulant is-121 ℃, 0.5h, the water-soluble simulant is-100 ℃ or the reflux temperature is 2 h'; the second step is "storage at room temperature or below 180 day" or more, i.e. "60 ℃, 10 day". And after the migration test is finished, fully and uniformly mixing the simulants obtained in the migration test for later use.
2) For a water-based simulant (4% acetic acid, 10% ethanol and 50% ethanol) test solution, 10mL of the simulant test solution obtained in the migration test is transferred into a 50mL screw-capped test tube, a proper amount of neopentyl glycol standard solution is rapidly added, and thus a plurality of sample solutions with different matrixes are taken to carry out different labeling operations for a plurality of times, so that labeled samples with the concentrations of 0.05, 0.25 and 5.0mg/L are respectively obtained. And (4) pretreating the water-based simulant test solution according to the step S21 to obtain a sample solution to be pretreated for GC-MS analysis.
3) For the oil-based (olive oil) simulant test solution, 10g (accurate to 0.01g) of the oil-based simulant test solution obtained in the migration test is weighed into a 100mL separating funnel, a proper amount of neopentyl glycol standard solution is rapidly added, and a plurality of samples are taken for a plurality of different labeling operations, so that the labeled samples with the concentrations of 0.05, 0.25 and 5.0mg/kg are respectively obtained. And (4) pretreating the oil-based simulant test solution according to the step S22 to obtain a sample solution to be pretreated for GC-MS analysis.
4) The qualitative results are as follows:
after the analysis experiment is completed, a peak which is consistent with the retention time of the characteristic ions of the target compound appears in the retention time window, and the characteristic ions of the target compound all appear in the sample mass spectrogram after the background is deducted, and the abundance ratio of the characteristic ions is consistent with that of the standard substance. The retention time of the neopentyl glycol phenylboronate serving as a detected target compound is 9.627min, and the retention time and abundance tolerance of all analysis samples are within the allowable deviation range.
5) Preparation of a standard solution: referring to the steps 1) to 5) of quantitative analysis of neopentyl glycol in the pretreated sample solution by using a GC-MS analyzer in the above embodiments, the detailed description thereof is omitted.
6) Standard curve linear equation, correlation coefficient (R)2) The test results and precision are shown in table three:
watch III
From the above results, it can be seen that the method of the present invention has a good linear relationship (R)2Not less than 0.995), the detection limit of the neopentyl glycol method in 4 food simulants can reach 0.05mg/kg, and the normalized recovery rate under the three concentration levels of 0.05mg/L, 0.25mg/L and 5mg/L is 83-116%, and the Relative Standard Deviation (RSD) is 3.4-13.3%, which meets the requirements of national relevant standards.
FIG. 3 is a chromatogram of neopentyl glycol derivatized product (neopentyl glycol phenylborate) from various mimetics, showing that the baseline of the instrument is stable and the response is high; FIG. 4 is a characteristic ion mass spectrum of a neopentyl glycol derivative product (neopentyl glycol phenylboronate).
While preferred embodiments of the present application have been described, additional variations and modifications of these embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the true scope of the embodiments of the application.
Finally, it should also be noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or terminal that comprises the element.
The method for determining the neopentyl glycol migration amount in the food contact material and the product provided by the application is described in detail, and the principle and the implementation mode of the application are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. A method for determining the migration of neopentyl glycol in food contact materials and articles, comprising the steps of: sampling; pretreating and detecting the migration quantity of a target object in the pretreated sample solution;
wherein the pretreatment step comprises:
when the sample is a water-based simulant test solution, mixing the sample with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated;
or;
when the sample is an oil-based simulant test solution, mixing the sample with a second extracting agent, carrying out oscillation treatment for a second designated time, and after standing and layering, obtaining a lower-layer phase solution as an extraction liquid; mixing the extract with phenylboronic acid to obtain a first solution; adding sodium chloride solid and a first extracting agent into the first solution, carrying out oscillation treatment for a first specified time, standing for layering, taking supernatant, mixing with a dehydrating agent, and dehydrating to obtain a sample solution to be pretreated;
the method comprises the following steps of (1) detecting the migration amount of a target substance in a pretreated sample solution, wherein the target substance in the pretreated sample solution is neopentyl glycol phenylboronate, and the step of detecting the migration amount of the target substance in the pretreated sample solution comprises the following steps:
and determining the content of neopentyl glycol phenylboronate by a GC-MS analyzer, and determining the migration amount of neopentyl glycol according to the content of neopentyl glycol phenylboronate.
2. The method of claim 1, wherein the step of calculating the neopentyl glycol content by measuring the neopentyl glycol phenylboronate content with a GC-MS analyzer comprises the following chromatographic conditions:
after the sample solution to be pretreated is placed into a chromatographic column, maintaining the temperature of the chromatographic column at 60 ℃ for 2min, and recording the chromatographic change in real time;
raising the temperature of the chromatographic column to 180 ℃ at a temperature rise rate of 15 ℃/min, and recording the chromatographic change in real time;
raising the temperature of the chromatographic column to 300 ℃ at a temperature raising speed of 30 ℃/min, maintaining the temperature of the chromatographic column at 300 ℃ for 1min, and recording the chromatographic change in real time.
3. The method of claim 2, wherein the step of calculating the neopentyl glycol content by measuring the neopentyl glycol phenylboronate content with a GC-MS analyzer comprises the mass spectrometry conditions of:
mass spectrum interface temperature: 300 ℃;
ion source temperature: 230 ℃;
quadrupole temperature: 150 ℃;
mass spectrometry scan mode: selecting an ion scan and a full scan;
quantification of neopentyl glycol phenylboronate: m/z 105; and (3) qualitative ion: m/z 190, m/z56, m/z 77.
4. The method of claim 1 wherein the first extractant is at least one of toluene, isooctane, n-hexane, n-heptane, and ethyl acetate; the second extracting agent is at least one of toluene, isooctane, n-hexane, n-heptane and ethyl acetate.
5. The method of claim 4 wherein the volume ratio of said sample to said first extractant is 2 mL: 1 mL.
6. The method of claim 4 wherein the volume ratio of said sample to said second extractant is 1 mL: 1 mL.
7. The method of claim 1 wherein the volume ratio of said sample to said derivatizing agent is 10 mL: 1 mL.
8. The method of claim 1, wherein the mass ratio of the phenylboronic acid to the sodium chloride solid to the first extractant is 1 mL: 2 g: 5 mL.
9. The method of claim 1 wherein the water-based food simulant sample solution is at least one of 4% acetic acid, 10% ethanol, and 50% ethanol, respectively; the oil-based food simulant test solution is olive oil.
10. The method for determining neopentyl glycol migration volume in food contact materials and articles according to any one of claims 1 to 9, wherein said first specified time is 30 min; the second designated time is 2 min.
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