CN110133121B - Method for simultaneously measuring migration amounts of ethylenediamine, propylenediamine and hexamethylenediamine in food contact material and product - Google Patents
Method for simultaneously measuring migration amounts of ethylenediamine, propylenediamine and hexamethylenediamine in food contact material and product Download PDFInfo
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- CN110133121B CN110133121B CN201910317506.8A CN201910317506A CN110133121B CN 110133121 B CN110133121 B CN 110133121B CN 201910317506 A CN201910317506 A CN 201910317506A CN 110133121 B CN110133121 B CN 110133121B
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- 238000013508 migration Methods 0.000 title claims abstract description 56
- 230000005012 migration Effects 0.000 title claims abstract description 56
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- 239000007864 aqueous solution Substances 0.000 claims description 4
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- 239000012071 phase Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 8
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- XPDXVDYUQZHFPV-UHFFFAOYSA-N Dansyl Chloride Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1S(Cl)(=O)=O XPDXVDYUQZHFPV-UHFFFAOYSA-N 0.000 description 2
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- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 1
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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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for simultaneously measuring the migration amounts of ethylenediamine, propylenediamine and hexamethylenediamine in food contact materials and products, which is characterized by comprising the steps of obtaining a food simulant test solution from the food contact materials and the food simulants through a migration experiment; placing the food simulant test solution into a plastic tube, adding a hydrochloric acid phenyl isothiocyanate acetonitrile solution and a triethylamine acetonitrile solution, uniformly mixing by vortex, carrying out water bath, and centrifuging a filter membrane; making a standard curve; liquid chromatography separation and mass spectrometry detection; and finally, calculating the concentrations of the ethylenediamine, the 1, 2-propanediamine and the 1, 6-hexanediamine in the sample solution by using a standard curve, and obtaining the migration amounts of the ethylenediamine, the 1, 2-propanediamine and the 1, 6-hexanediamine in the food contact material and the food contact material according to the calculation method of the migration amounts of the substances to be detected in the food contact material and the food contact material.
Description
Technical Field
The invention relates to a method for simultaneously determining the migration amounts of ethylenediamine, propylenediamine and hexamethylenediamine in food contact materials and products based on liquid chromatography-tandem mass spectrometry.
Background
Ethylene diamine, 1, 2-propane diamine and 1, 6-hexane diamine are important chemical raw materials, have wide application in production and life, and are commonly used for producing daily necessities such as food contact materials. The development of the detection method for the migration quantity of the ethylenediamine, the 1, 2-propanediamine and the 1, 6-hexanediamine in the food contact material has important practical significance for guaranteeing the food safety of people.
Ethylenediamine is a colorless transparent viscous liquid, has ammonia odor, is toxic and flammable, and is widely applied to the industries of manufacturing organic compounds, high molecular compounds, medicines, dyes, pesticides and the like. The existing detection method of ethylenediamine mainly comprises a gas phase method and a liquid phase method. In the gas phase method, the ethylenediamine is directly injected, the detection limit can be as low as 0.02mg/L, but the ethylenediamine in the method has fast peak generation and is easy to be interfered. The liquid chromatography determination, it is reported that ethylenediamine is derived from dansyl chloride, and the detection limit is 0.5mg/L after the liquid chromatography separation by using an ultraviolet detector.
1, 2-propanediamine is a colorless, pure liquid, with strong basicity and strong hygroscopicity, and produces white smoke when in contact with air. Is easily soluble in water, ethanol and chloroform, and insoluble in diethyl ether and benzene. The 1, 2-propane diamine is used for producing mineral dressing medicament, metal deactivator, aviation resin curing agent and rubber vulcanization accelerator in industry, and is used for producing intermediate of anticancer medicine propane imine in medicine industry. The detection method of the 1, 2-propane diamine is less, and no relevant literature report exists in China.
1, 6-hexanediamine is a strong organic base, flammable, toxic, corrosive. 1, 6-hexamethylenediamine is mainly used for synthesizing nylon 66 and 610 resins, and also used for synthesizing polyurethane resins, ion exchange resins and hexamethylene diisocyanate, and used as curing agents, organic crosslinking agents and the like of urea resins, epoxy resins and the like. In the existing detection method of 1, 6-hexamethylenediamine, liquid chromatography is reported, hexamethylenediamine is derived by dansyl chloride, and the detection limit is 10ng/mL after liquid chromatography separation by fluorescence detection. At present, no relevant research report about a method for simultaneously determining the migration amounts of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine in food contact materials and products based on a liquid chromatography-tandem mass spectrometry is disclosed at home and abroad.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for simultaneously determining the migration quantities of ethylenediamine, propylenediamine and hexamethylenediamine in food contact materials and products based on liquid chromatography-tandem mass spectrometry, which is simple and convenient to operate, strong in anti-interference capability and low in detection limit.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for simultaneously measuring the migration amounts of ethylenediamine, propylenediamine and hexamethylenediamine in food contact materials and products comprises the following steps:
(1) sample processing
The food simulant test solution is obtained by a migration experiment of a food contact material and a food simulant; placing the food simulant test solution into a plastic tube, adding 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile solution, uniformly mixing for 1min in a vortex manner, carrying out water bath at the temperature of 80 ℃ for 1h, centrifuging, filtering by a 0.22 mu M filter membrane, and feeding a sample on a machine, wherein the volume ratio of the food simulant test solution to the hydrochloric acid to the phenyl isothiocyanate acetonitrile solution to the triethylamine acetonitrile solution is 2: 98: 25: 25;
(2) standard Curve preparation
Sucking mixed standard solutions with the concentration of 10 mu g/mL of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine, fixing the volume by using 0.1M hydrochloric acid, and preparing the mixed standard solutions into mixed standard solutions with the concentration of 100ng/mL, 200ng/mL, 500ng/mL, 1000ng/mL and 2000ng/mL respectively; placing a standard solution into a plastic tube, adding 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile solution, uniformly mixing for 1min in a vortex manner, carrying out water bath at 80 ℃ for 1h, centrifuging, filtering by a 0.22-micron filter membrane, feeding a sample on a machine, taking the concentration as a horizontal coordinate and an instrument response value as a vertical coordinate, making a matrix and standard curve as a basis for quantifying the concentration of a substance to be detected in a sample treatment solution, wherein the volume ratio of the standard solution to the hydrochloric acid to the phenyl isothiocyanate acetonitrile solution to the triethylamine acetonitrile solution is 2: 98: 25: 25, response = standard peak area/standard mass;
(3) liquid chromatography separation
Liquid chromatography flow rate: 0.300 mL/min;
mobile phase: the phase A is acetonitrile, the phase B is ammonium acetate-acetic acid solution, and the mobile phase gradient elution procedure is shown in table 1;
liquid chromatography analysis time: 12 min;
sample introduction amount: 5 mu L of the solution;
temperature of the chromatographic column: 30 ℃;
compound retention time: ethylene diamine: 5.81 min; 1, 2-propanediamine: 6.90 min; 1, 6-hexamethylenediamine: 8.98 min;
table 1 flow phase ratio example
(4) Mass spectrometric detection
An ion source: electrospray ion source (ESI);
the detection mode is as follows: multiple Reaction Monitoring (MRM);
the scanning mode is as follows: a positive ion mode;
capillary voltage: positive ion mode, 4000V;
ion source temperature: 150 ℃;
flow rate of drying gas: 5L/min;
atomizing gas pressure: 45 psi;
temperature of sheath gas: 350 ℃; sheath gas (N)2) Flow rate: 8L/min; other mass spectral parameters are shown in table 2;
TABLE 2 Mass Spectrometry parameters
(5) Concentration calculation method
And calculating the concentrations of the ethylenediamine, the propylenediamine and the hexamethylenediamine in the sample solution according to the standard curve, and obtaining the migration amounts of the ethylenediamine, the 1, 2-propylenediamine and the 1, 6-hexamethylenediamine in the food contact material and the product according to the calculation method of the migration amounts of the substances to be detected in the food contact material and the product.
The food simulant described in step (1) comprises a 4% volume fraction acetic acid solution, a 10% volume fraction ethanol aqueous solution, a 20% volume fraction ethanol solution, a 50% volume fraction ethanol solution, a 95% volume fraction ethanol aqueous solution, a 4% volume fraction acetic acid solution and vegetable oil.
The preparation method of the ammonium acetate-acetic acid solution in the step (3) is as follows: 1.54g of ammonium acetate was dissolved in 500mL of water, 10mL of glacial acetic acid was added, and the volume was set to 1000 mL.
The specific calculation method in the step (4) is as follows: to adopt mg/dm2The migration amount of the test solution of each food simulant is determined by
Calculating, wherein X is the migration amount of the object to be detected, namely ethylene diamine, 1, 2-propylene diamine or 1, 6-hexamethylene diamine, and the unit is mg/dm2(ii) a c is the content of ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the food simulant test solution obtained by the migration test, and the unit is mg/L or mg/kg; c0The content of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine in the blank food simulant is mg/L or mg/kg; v is the volume or mass of the food simulant in the migration test, the unit is L or kg, and the blank test solution is the test solution of the food simulant which is not contacted with the food contact material; s is the area of contact between the sample and the food simulant in the migration test, and is expressed in dm2；
When mg/kg is used as a unit, the migration amount of the test solution of various food simulants is determined according to
Calculation of, wherein X1Is the substance to be detected, such as ethylenediamine, 1, 2-propanediamine orThe migration amount of the 1, 6-hexanediamine is mg/kg; c is the content of the objects to be detected, namely ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the food simulant test solution obtained by the migration test, and the unit is mg/L or mg/kg; c0The content of ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the blank food simulant is mg/L or mg/kg; v is the volume or mass of the food simulant in the migration test, and the unit is L or kg; s is the area of contact between the sample and the food simulant in the migration test, and is expressed in dm2(ii) a F is the ratio S/V of the contact area S of the food contact material and the product to the mass of the food in contact, and has a unit dm2/kg or dm2/L。
Compared with the prior art, the invention has the advantages that: the invention discloses a method for simultaneously determining the migration amounts of ethylenediamine, 1, 2-propanediamine and 1, 6-hexamethylenediamine in food contact materials and products based on a liquid chromatography-tandem mass spectrometry, wherein in the presence of triethylamine, the ethylenediamine, 1, 2-propanediamine and 1, 6-hexamethylenediamine react with phenyl isothiocyanate to generate a substance capable of generating ions in an electrospray source mass spectrometry (ESI source), the substance is subjected to liquid chromatography separation, electrospray source mass spectrometry detection and external standard method quantification, and the method can effectively solve the problem of accurately detecting the contents of ethylenediamine, 1, 2-propanediamine and 1, 6-hexamethylenediamine, and has the advantages of simple operation, stable method, strong capability and low detection limit interference resistance.
Drawings
FIG. 1 is a 10ng/mL chromatogram of ethylenediamine, 1, 2-propanediamine, and 1, 6-hexanediamine.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Reagent preparation and apparatus
0.1mol/L phenyl isothiocyanate acetonitrile solution: 1.35g of phenyl isothiocyanate was weighed and made up to 100mL with acetonitrile.
1mol/L triethylamine acetonitrile solution: 10.1g triethylamine was weighed and made up to 100mL with acetonitrile.
0.1M hydrochloric acid: 0.86mL of concentrated HCl was dissolved in a 100mL volumetric flask.
Preparing a mixed standard solution of 10 mu g/mL of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine: mixing 100 mu L of 1mg/mL ethylenediamine, 1mg/mL1, 2-propanediamine and 1mg/mL1, 6-hexanediamine standard solution, and diluting to 10mL by acetonitrile, wherein the 1mg/mL ethylenediamine standard solution is prepared by: weighing 10 mg of ethylenediamine standard substance, and fixing the volume to 10mL by using acetonitrile; 1mg/mL1, 2-propanediamine standard solution preparation: weighing 10 mg of 1, 2-propane diamine standard substance, and fixing the volume to 10mL by using acetonitrile; 1mg/mL1, 6-hexanediamine standard solution preparation: weighing 10 mg of 1, 6-hexanediamine standard substance, and diluting to 10mL with acetonitrile; the purity of the ethylene diamine, the 1, 6-hexamethylene diamine and the 1, 2-propane diamine is more than 99 percent.
The instrument comprises the following steps: liquid chromatography mass spectrometer: agilent1290 liquid chromatography, column: phenomenex Luma C18 (150 mm. times.2 mm, 3 μm) or equivalent; agilent 6460 mass spectrometer.
2. The method for simultaneously measuring the migration amounts of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine in food contact materials and products has the following detection principle: in the presence of triethylamine, ethylenediamine, 1, 2-propanediamine, 1, 6-hexamethylenediamine and phenyl isothiocyanate react to generate a substance capable of generating ions in electrospray source mass spectrometry (ESI source), and the substance is subjected to liquid chromatography separation, electrospray source mass spectrometry detection and external standard quantification. The method comprises the following specific steps:
(1) sample processing
The food simulant test solution is obtained by a migration experiment of a food contact material and a food simulant, and comprises a water-based food simulant test solution and an oil-based food simulant test solution (the food simulant test solution is obtained from the migration experiment according to the requirements of GB31604.1 and GB5006.156 and should be refrigerated and stored in a refrigerator in a dark place); putting 20 mu L of food simulant test solution into a 15mL plastic tube, adding 980 mu L of 0.1M hydrochloric acid, 250 mu L of 0.1mol/L phenyl isothiocyanate acetonitrile solution and 250 mu L of 1mol/L triethylamine acetonitrile solution, vortex and uniformly mixing for 1min, carrying out water bath at 80 ℃ for 1h, centrifuging, filtering through a 0.22 mu M filter membrane, and feeding the sample on the machine;
(2) standard Curve preparation
Sucking mixed standard solutions with the concentration of 10 mu g/mL of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine, fixing the volume by using 0.1M hydrochloric acid, and preparing the mixed standard solutions into mixed standard solutions with the concentration of 100ng/mL, 200ng/mL, 500ng/mL, 1000ng/mL and 2000ng/mL respectively; putting 20 mu L of standard solution into a 15mL plastic tube, adding 980 mu L of hydrochloric acid, 250 mu L of phenyl isothiocyanate acetonitrile solution and 250 mu L of triethylamine acetonitrile solution, mixing uniformly for 1min in a vortex mode, carrying out water bath at 80 ℃ for 1h, centrifuging, filtering a 0.22 mu M filter membrane, loading the sample on a machine, taking the concentration as a horizontal coordinate and an instrument response value (the response value = peak area of the standard product/mass of the standard product) as a vertical coordinate, and taking a matrix and standard curve as a basis for quantifying the concentration of the substance to be detected in the sample treatment solution;
(3) liquid chromatography separation
A chromatographic column: phenomenex Luma C18 (150 mm. times.2 mm, 3 μm) or equivalent;
liquid chromatography flow rate: 0.300 mL/min;
mobile phase: the phase A is acetonitrile, the phase B is ammonium acetate-acetic acid solution, and the mobile phase gradient elution procedure is shown in table 1; the preparation method of the ammonium acetate-acetic acid solution comprises the following steps of dissolving 1.54g of ammonium acetate in 500mL of water, adding 10mL of glacial acetic acid, and metering the volume to 1000 mL;
liquid chromatography analysis time: 12 min;
sample introduction amount: 5 mu L of the solution;
temperature of the chromatographic column: 30 ℃;
as shown in fig. 1, compound retention time: ethylene diamine: 5.81 min; 1, 2-propanediamine: 6.90 min; 1, 6-hexamethylenediamine: 8.98 min;
table 1 flow phase ratio example
(4) Mass spectrometric detection
An ion source: electrospray ion source (ESI);
the detection mode is as follows: multiple Reaction Monitoring (MRM);
the scanning mode is as follows: a positive ion mode;
capillary voltage: positive ion mode, 4000V;
ion source temperature: 150 ℃;
flow rate of drying gas: 5L/min;
atomizing gas pressure: 45 psi;
temperature of sheath gas: 350 ℃; sheath gas (N)2) Flow rate: 8L/min; other mass spectral parameters are shown in table 2;
TABLE 2 Mass Spectrometry parameters
(5) Concentration calculation method
The concentrations of ethylenediamine, 1, 2-propylenediamine and 1, 6-hexamethylenediamine in the sample solution were calculated from the standard curve, and the migration amounts of ethylenediamine, 1, 2-propylenediamine and 1, 6-hexamethylenediamine in the food contact material and the product were obtained by the calculation method of the migration amounts of the substances to be measured in the food contact material and the product (calculation according to GB 5009.156). The specific calculation method is as follows: to adopt mg/dm2The migration amount of the test solution of each food simulant is determined by
Calculating, wherein X is the migration amount of the object to be detected, namely ethylene diamine, 1, 2-propylene diamine or 1, 6-hexamethylene diamine, and the unit is mg/dm2(ii) a c is the content of ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the food simulant test solution obtained by the migration test, and the unit is mg/L or mg/kg; c0The content of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine in the blank food simulant is mg/L or mg/kg; v is the volume or mass of the food simulant in the migration test, the unit is L or kg, and the blank test solution is the test solution of the food simulant which is not contacted with the food contact material; s is the area of contact between the sample and the food simulant in the migration test, and is expressed in dm2；
When mg/kg is used as a unit, the migration amount of the test solution of various food simulants is determined according to
Calculation of, wherein X1The migration amount of an object to be detected, namely ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine is mg/kg; c isThe content of the objects to be detected, namely ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine, in the food simulant test solution obtained by the migration test is mg/L or mg/kg; c0The content of ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the blank food simulant is mg/L or mg/kg; v is the volume or mass of the food simulant in the migration test, and the unit is L or kg; s is the area of contact between the sample and the food simulant in the migration test, and is expressed in dm2(ii) a F is the ratio S/V of the contact area S of the food contact material and the product to the mass of the food in contact, and has a unit dm2/kg or dm2/L。
3. Method verification test
3.1 detection Limit
Diluting ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine standard products step by step, taking 20 mu L, putting the 20 mu L into a 15mL plastic tube, adding 980 mu L of 0.1M hydrochloric acid, 250 mu L of 0.1mol/L phenylisothiocyanate acetonitrile solution and 250 mu L of 1mol/L triethylamine acetonitrile solution, uniformly mixing by vortex for 1min, carrying out water bath at 80 ℃ for 1h, centrifuging, filtering by a 0.22 mu M filter membrane, and carrying out sample feeding on a machine for measurement to obtain the detection limits of the three substances. The results were: 25 ng/mL of ethylenediamine; 25 ng/mL of 1, 2-propane diamine; 1, 6-hexanediamine 25 ng/mL.
3.2 Standard Curve Range:
and (3) preparing standard curves of the ethylenediamine, the 1, 2-propanediamine and the 1, 6-hexanediamine, pretreating the sample according to the method of 3.1, and then feeding the sample into a machine for testing to obtain the standard curve ranges of the three substances.
Linear range of ethylenediamine: 0.05-10 μ g/mL, linear correlation R2>0.99；
Linear range of 1, 2-propanediamine: 0.05-10 μ g/mL, linear correlation R2>0.99；
Linear range of 1, 6-hexanediamine: 0.05-10 μ g/mL, linear correlation R2>0.99；
3.3 method precision and recovery
6 parts of samples respectively containing ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine standard substances with the concentration of 500ng/mL are pretreated according to the method 3.1, and then are loaded on a machine for sample injection and measurement, so that the precision of the three substances in the water sample measured by the method is obtained, and the results are shown in Table 3.
TABLE 3 determination of the precision of ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine in water samples
The concentrations of ethylene diamine, 1, 2-propane diamine and 1, 6-hexane diamine standard substances are all 500ng/mL respectively added into various food analog samples, and after pretreatment is carried out according to the method 3.1, the samples are loaded on a machine for measurement, so that the recovery rates of the three substances in the water sample measured by the method are obtained, and the results are shown in Table 4.
TABLE 4 determination of the recovery of ethylenediamine, 1, 2-propylenediamine, 1, 6-hexamethylenediamine in a sample of water
As can be seen from the above tables 3 and 4, the method for simultaneously measuring the migration amounts of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine in the food contact material and the food product based on the liquid chromatography tandem mass spectrometry, which is established by the invention, has good precision and recovery rate.
3.4 advantages of the method:
the method has the following capacity of resisting disturbance: the method adopts triple quadrupole mass spectrometry for detection, can detect three substances simultaneously, has strong anti-interference capability, has the following formula of disubstituted organic amine and phenyl isothiocyanate,
the above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (3)
1. A method for simultaneously measuring the migration amounts of ethylenediamine, propylenediamine and hexamethylenediamine in food contact materials and products is characterized by comprising the following steps:
(1) sample processing
The food simulant test solution is obtained by a migration experiment of a food contact material and a food simulant; placing the food simulant test solution into a plastic tube, adding 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile solution, uniformly mixing for 1min in a vortex manner, carrying out water bath at the temperature of 80 ℃ for 1h, centrifuging, filtering by a 0.22 mu M filter membrane, and feeding a sample on a machine, wherein the volume ratio of the food simulant test solution to the hydrochloric acid to the phenyl isothiocyanate acetonitrile solution to the triethylamine acetonitrile solution is 2: 98: 25: 25;
(2) standard Curve preparation
Sucking mixed standard solutions with the concentration of 10 mu g/mL of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine, fixing the volume by using 0.1M hydrochloric acid, and preparing the mixed standard solutions into mixed standard solutions with the concentration of 100ng/mL, 200ng/mL, 500ng/mL, 1000ng/mL and 2000ng/mL respectively; placing a standard solution into a plastic tube, adding 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile solution, uniformly mixing for 1min in a vortex manner, carrying out water bath at 80 ℃ for 1h, centrifuging, filtering by a 0.22-micron filter membrane, feeding a sample on a machine, taking the concentration as a horizontal coordinate and an instrument response value as a vertical coordinate, making a matrix and standard curve as a basis for quantifying the concentration of a substance to be detected in a sample treatment solution, wherein the volume ratio of the standard solution to the hydrochloric acid to the phenyl isothiocyanate acetonitrile solution to the triethylamine acetonitrile solution is 2: 98: 25: 25;
(3) liquid chromatography separation
Mobile phase: the phase A is acetonitrile, the phase B is ammonium acetate-acetic acid solution, and the liquid chromatography flow rate is as follows: 0.300 mL/min; sample introduction amount: 5 mu L of the solution; temperature of the chromatographic column: the preparation method of the ammonium acetate-acetic acid solution is as follows at 30 ℃: 1.54g ammonium acetate was dissolved in 500mL water, 10mL glacial acetic acid was added and the volume was brought to 1000mL and the mobile phase gradient elution procedure is shown in Table 1:
table 1 flow phase ratio example
(4) Mass spectrometric detection
An ion source: an electrospray ion source; the detection mode is as follows: monitoring multiple reactions; capillary voltage: positive ion mode, 4000V; ion source temperature: 150 ℃; flow rate of drying gas: 5L/min; atomizing gas pressure: 45 psi; temperature of sheath gas: 350 ℃; the flow rate of the sheath gas: 8L/min, wherein the mass spectrum parameters are shown in Table 2:
TABLE 2 Mass Spectrometry parameters
(5) Concentration calculation method
And calculating the concentrations of the ethylenediamine, the 1, 2-propanediamine and the 1, 6-hexanediamine in the sample solution according to the standard curve, and obtaining the migration amounts of the ethylenediamine, the 1, 2-propanediamine and the 1, 6-hexanediamine in the food contact material and the product according to the calculation method of the migration amounts of the substances to be detected in the food contact material and the product.
2. The method of claim 1 for simultaneously determining the amount of ethylene diamine, propylene diamine, and hexamethylene diamine migrating in food contact materials and articles, wherein: the food simulant described in step (1) comprises a 4% volume fraction acetic acid solution, a 10% volume fraction ethanol aqueous solution, a 20% volume fraction ethanol solution, a 50% volume fraction ethanol solution, a 95% volume fraction ethanol aqueous solution and vegetable oil.
3. The method for simultaneously measuring the migration amounts of ethylenediamine, propylenediamine, and hexamethylenediamine in food contact materials and products according to claim 1, wherein the specific calculation method in step (5) is as follows: to adopt mg/dm2The migration amount of the test solution of each food simulant is determined by
Calculating, wherein X is the migration amount of the object to be detected, namely ethylene diamine, 1, 2-propylene diamine or 1, 6-hexamethylene diamine, and the unit is mg/dm2(ii) a c food simulation from migration testThe content of ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the sample solution is mg/L or mg/kg; c0The content of ethylenediamine, 1, 2-propanediamine and 1, 6-hexanediamine in the blank food simulant is mg/L or mg/kg; v is the volume or mass of the food simulant in the migration test, the unit is L or kg, and the blank test solution is the test solution of the food simulant which is not contacted with the food contact material; s is the area of contact between the sample and the food simulant in the migration test, and is expressed in dm2；
When mg/kg is used as a unit, the migration amount of the test solution of various food simulants is determined according to
Calculation of, wherein X1The migration amount of an object to be detected, namely ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine is mg/kg; c is the content of the objects to be detected, namely ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the food simulant test solution obtained by the migration test, and the unit is mg/L or mg/kg; c0The content of ethylenediamine, 1, 2-propanediamine or 1, 6-hexanediamine in the blank food simulant is mg/L or mg/kg; v is the volume or mass of the food simulant in the migration test, and the unit is L or kg; s is the area of contact between the sample and the food simulant in the migration test, and is expressed in dm2(ii) a F is the ratio of the contact area S of the food contact material and the product to the mass of the food in contact, and is expressed in dm2/kg or dm2/L。
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| CN111007180A (en) * | 2019-12-29 | 2020-04-14 | 无锡殷达尼龙有限公司 | Method for quantitatively detecting aliphatic diamine by using high performance liquid chromatography |
| CN111077255A (en) * | 2020-01-10 | 2020-04-28 | 南京市产品质量监督检验院 | Method for detecting migration volume of 4, 4'-biphenol and 4,4' -dichlorodiphenyl sulfone in PPSU (polypropylene sulfone) milk bottle |
| CN111289675B (en) * | 2020-03-11 | 2022-08-23 | 宁波市疾病预防控制中心 | Method for measuring migration quantity of laurolactam in food contact material |
| CN111879861B (en) * | 2020-04-03 | 2021-09-28 | 江南大学 | Method for accurately detecting content of hexamethylene diamine in fermentation liquor |
| CN116660398B (en) * | 2023-03-31 | 2024-01-23 | 南京海关危险货物与包装检测中心 | Food contact material and method for detecting migration quantity of N-ethyl o-toluenesulfonamide in product |
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