CN114755316B - Method for screening dangerous substances in food contact material and application - Google Patents

Method for screening dangerous substances in food contact material and application Download PDF

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CN114755316B
CN114755316B CN202210196209.4A CN202210196209A CN114755316B CN 114755316 B CN114755316 B CN 114755316B CN 202210196209 A CN202210196209 A CN 202210196209A CN 114755316 B CN114755316 B CN 114755316B
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bisphenol
phthalate
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ether
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CN114755316A (en
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李泽荣
黄晓钢
潘云飞
熊小婷
凌光耀
饶璞
陈意光
宋梓锋
佘文勋
张沛林
郭旭东
刘德云
张胡松
谢文缄
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GUANGZHOU QUALITY SUPERVISION AND TESTING INSTITUTE
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
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    • G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
    • G01N30/724—Nebulising, aerosol formation or ionisation
    • G01N30/7266—Nebulising, aerosol formation or ionisation by electric field, e.g. electrospray
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N2030/042—Standards
    • G01N2030/047—Standards external

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Abstract

The invention relates to a method for screening dangerous substances in food contact materials and application thereof. The method comprises the following steps: preparing a standard solution: preparing a reference substance of risk substances, wherein the risk substances are 139 substances selected from bisphenol A-diglycidyl ether and the like; preparing a test solution: taking a contact material as a test sample, and performing pretreatment to obtain a test sample solution; and (3) liquid chromatography-mass spectrometry detection: detecting the standard working solution and the sample solution by adopting a high performance liquid chromatography-quadrupole flight time mass spectrometer respectively; and (3) result judgment: and comparing the detection result of the sample solution with the detection result of the standard working solution to obtain the screening result of the risk substance. The method optimizes chromatographic determination conditions and mass spectrometry determination conditions, has detection limit of each compound of 0.1-400 mug/L, can evaluate risk substances existing in food contact materials more efficiently and comprehensively, provides good technical support for quality control and safety monitoring of food contact materials and products, and has high application value.

Description

Method for screening dangerous substances in food contact material and application
Technical Field
The invention relates to the field of material analysis, in particular to a method for screening dangerous substances in food contact materials and application thereof.
Background
The food contact material is in close contact with the food, and its ingredients may migrate into the contents to affect food safety, so the food contact material is also called an indirect food additive. The exposure risk of the food contact material to human body is characterized by three characteristics of passivity, unavoidable property and long-term property, and trace amounts of the risk substances can cause great potential safety hazards to the health and safety of consumers. Food safety events caused by food contact materials have been frequent in recent years, such as: bisphenol a events in the baby bottle, phthalate plasticizer events in plastic food packaging products, and the like, all sound alarms for safe use of food contact materials. Many risk substances in food contact materials are not identified, and most of the current detection methods of the food contact material safety risk substances are only aimed at single substances or one type of substances, and technical researches of simultaneous screening of multiple types of risk substances are rarely considered, which is insufficient for protecting consumers.
The liquid chromatograph-quadrupole time-of-flight mass spectrometer is a mass spectrometry technique which uses liquid chromatograph as a separation system, electrospray or normal pressure chemical ionization source as ionization mode, and quadrupole serial time-of-flight as a mass analyzer. The multi-dimensional analysis parameter setting, high sensitivity, high resolution and high acquisition speed of the method endow the method with extremely high chemical component acquisition and analysis capability (tens to thousands of chemical components are acquired by one-needle sample injection), and the method is widely applied to detection and research directions of pesticide residues, veterinary drug residues, illegal additives screening, soluble matters and extractables in food/drug packages, unintentional additives, high-attention substance screening, cosmetics forbidden substances screening, traditional Chinese medicine chemical component identification, drug metabolism, proteomics and the like in combination with huge data processing functions and statistical analysis functions of software.
Therefore, it is desirable to provide a method for more comprehensively screening dangerous materials in food contact materials based on liquid chromatography-quadrupole time-of-flight mass spectrometry.
Disclosure of Invention
Based on this, it is necessary to provide a method for screening dangerous substances in food contact materials in view of the above-mentioned problems.
A method of screening for risk materials in a food contact material comprising the steps of:
preparing a standard solution: preparing a reference substance of the risk substance by using a solvent to prepare a standard working solution; the risk substance includes: bisphenol A-diglycidyl ether, bisphenol A- (2, 3-dihydroxypropyl) glycidyl ether, bisphenol A- (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether, bisphenol A-bis (2, 3-dihydroxypropyl) ether, bisphenol A- (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F-diglycidyl ether, bisphenol F-bis (3-chloro-2-hydroxypropyl) ether, bisphenol F-bis (2, 3-dihydroxypropyl) ether, 3Ring NOGE,4Ring NOGE,5Ring NOGE,6Ring NOGE,cyclo-di-BADGE, dimethyl phthalate, diethyl phthalate, diallyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, dibutyl phthalate, di (2-butoxy) phthalate, di (2, 6-diphenyl phthalate, di-n-butyl phthalate, di-2-n-butyl phthalate, di-2-butyl phthalate, di-n-butyl phthalate, di-2-butyl phthalate, 2, 4-dimethylaniline, 2, 6-dimethylaniline, o-aminoazotoluene, p-aminoazobenzene, o-methoxyaniline, 4 '-methylene-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -dimethylbenzidine, 3 '-dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4 '-diaminodiphenyl sulfide, 4-chloro-o-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4 '-diaminodiphenyl methane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), imazalil, thiabendazole, methylisothiazolinone, 1, 2-benzisothiazol-3-one, methyl chloroisothiazolinone, cyproconazole, propiconazole, tebuconazole, imidacloprid, carbendazim, 2-octyl-4-isothiazolin-3-one, iodopropynyl butylcarbamate, melamine, benzomelamine, caprolactam, isophoronediamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexamethylenediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, diethylhexyl adipate, cyclohexane 1, 2-dicarboxylic acid diisononyl ester, acetyl tributyl citrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, UV absorber 320, UV absorber 328, UV absorber 3039, UV-9, benzophenone-12, benzophenone-6, 2- (dimethoxy) ethyl methacrylate, azacyclotridin-2-one, 1, 4-butanediol glycidyl ether, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, dichlorophenol, o-phenylphenol, dodecylphenol, 4-tert-octylphenol, nonylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, hexafluorobisphenol A, bisphenol E, bisphenol TMC, bisphenol M, bisphenol OPPA, 4' -dihydroxytetraphenyl methane, UV-24, UV-0,4,4' -dihydroxybenzophenone, perfluorobutyric acid, perfluorovaleric acid, perfluorocaproic acid, perfluoroheptanoic acid, perfluorocaprylic acid, perfluorononanoic acid, perfluorocapric acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-chlorom-xylenol, pentachlorophenol, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid, 4' -dihydroxytetraphenylmethane, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-chlorom-xylenol, 4-chloro-3-cresol, terephthalic acid and 1, 4-cyclohexanedicarboxylic acid;
Preparing a test solution: taking a contact material as a test sample, and performing pretreatment to obtain a test sample solution;
and (3) liquid chromatography-mass spectrometry detection: detecting the risk substances by adopting a high performance liquid chromatography-quadrupole flight time mass spectrometer respectively for the standard working solution and the sample solution;
and (3) result judgment: and comparing the detection result of the sample solution with the detection result of the standard working solution to obtain the screening result of the risk substance.
The invention relates to a screening method of 139 risk substances in food contact materials, which is a screening method for simultaneously detecting most risk substances in the food contact materials, wherein part of compounds are risk substances (such as phthalates and aromatic amines) which pay attention to more, and part of compounds are risk substances (such as Cyclo-di-BADGE, benzomelamine and the like) which establish a related detection method for the first time.
In one embodiment, the risk substance is selected from: bisphenol A diglycidyl ether, bisphenol A (2, 3-dihydroxypropyl) glycidyl ether, bisphenol A (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether, bisphenol A bis (2, 3-dihydroxypropyl) ether, bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F diglycidyl ether, bisphenol F bis (3-chloro-2-hydroxypropyl) ether, bisphenol F bis (2, 3-dihydroxypropyl) ether, cyclo-di-BADGE, 3ring NOGE, 4ring NOGE, 5ring NOGE, 6ring NOGE, dimethyl phthalate, imazalil, thiabendazole cyproconazole, propiconazole, tebuconazole, imidacloprid, carbendazim, iodopropynyl butylcarbamate, benzomelamine, caprolactam, diethyl hexyl adipate, diisononyl cyclohexane 1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, UV absorber 320, UV absorber 328, UV absorber 3039 (octocrylene), UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, 1, 4-butanediol glycidyl ether;
The following first chromatographic assay conditions were selected:
chromatographic column: hypersil GOLD TM ，100mm×0.4mm，3μm；
Mobile phase 1: a: according to 0.2mL formic acid: 1L of water is prepared, B: according to 0.156g of ammonium acetate: 0.2mL formic acid: 2mL of water: 200mL of isopropanol: 800mL of methanol is prepared;
elution procedure 1: the ratio of the flow rate to the mobile phase B is adjusted according to the following time points, and the ratio of the flow rate to the mobile phase B is in linear gradient change between the two time points;
the risk substance is selected from: diethyl phthalate, diallyl phthalate, diisobutyl/di-n-butyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, di-n-octyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene/2, 4-diaminotoluene 2, 4-dimethylaniline, 2, 6-dimethylaniline, o-aminoazotoluene, p-aminoazobenzene, o-methoxyaniline, 4' -methylene-bis- (2-chloroaniline), 3' -dimethyl-4, 4' -diaminodiphenylmethane, 3' -dimethylbenzidine, 3' -dimethoxybenzidine, 3' -dichlorobenzidine, para-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4' -diaminodiphenyl sulfide, 4-chlorophthaline, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4' -diaminodiphenyl methane, 4,4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazolin-3-one, methylchloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, melamine, isophoronediamine, 4' -methylenebis (2-methylcyclohexylamine), 1, 6-hexamethylenediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, di (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azatridecan-2-one;
The following second chromatographic assay conditions were selected:
chromatographic column: hypersil GOLD TM ，100mm×0.4mm，3μm；
Mobile phase 2: a: according to 0.2mL formic acid: 1L of water is prepared, B: according to 0.2mL formic acid: 1L of acetonitrile;
the elution procedure 1;
the risk substance is selected from: 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, bischlorophenol, o-phenylphenol, dodecylphenol, 4-tert-octylphenol, nonylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, hexafluorobisphenol A, bisphenol E, bisphenol TMC, bisphenol M, bisphenol OPPA, 4 '-dihydroxytetraphenylmethane, UV-24, UV-0, 4' -dihydroxybenzophenone, perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-xylenol, p-chloroisophthalic acid, p-xylene, and p-xylene;
the following third chromatography assay conditions were selected:
Chromatographic column: hypersil GOLD TM ，100mm×0.4mm，3μm；
Mobile phase 3: a: according to 0.1mL of ammonia: 1L of water is prepared, B: according to 0.1mL of ammonia: 1L of acetonitrile;
elution procedure 2: the ratio of the flow rate to the mobile phase B is adjusted according to the following time points, and the ratio of the flow rate to the mobile phase B is in linear gradient change between the two time points;
the mobile phase combinations selected in the present invention are the results of comparing the signal to noise ratio of each compound in the different flow combinations, and the linear range, preference. Specifically, the first chromatographic conditions are selected for the risk substance corresponding to the first chromatographic conditions, so that the first chromatographic conditions can be increased by [ M+NH ] 4 ] + For the signal-to-noise ratio of compounds of the predominant ionisation mode, part [ M+H] + The compound also has higher signal-to-noise ratio under the first chromatographic condition; for most aromatic amine compounds, the second chromatographic assay conditions can provide a higher signal to noise ratio; the first chromatographic condition and the second chromatographic condition can form better complementary action on the compound in positive ionization mode, so that the method can cover more risk substances; the third chromatography assay conditions may be responsive to the negatively ionized compound as set forth in the method. The addition of ammonium acetate in the mobile phase reduces the response (signal to noise ratio) of part of the compounds, and is therefore not Ammonium acetate was added to the chromatographic conditions.
In one embodiment, in the step of detecting the liquid chromatography-mass spectrometry, the following detection conditions are adopted: CAD GAS was set at 4-7psi, GAS1 and GAS2 were both set at 45-65psi, and the temperature was set at 500-600deg.C.
In one embodiment, the risk substance is selected from: bisphenol A diglycidyl ether, bisphenol A (2, 3-dihydroxypropyl) glycidyl ether, bisphenol A (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether, bisphenol A bis (2, 3-dihydroxypropyl) ether, bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F diglycidyl ether, bisphenol F bis (3-chloro-2-hydroxypropyl) ether, bisphenol F bis (2, 3-dihydroxypropyl) ether, cyclo-di-BADGE, 3ring NOGE, 4ring NOGE, 5ring NOGE, 6ring NOGE, dimethyl phthalate, imazalil, thiabendazole, cyproconazole, propiconazole, tebuconazole, and the like imidacloprid, carbendazim, iodopropynyl butylcarbamate, benzomelamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane 1, 2-dicarboxylate, tributyl acetylcitrate, trimethylol propane trimethacrylate, antioxidant 1098, antioxidant TH-1790, UV absorber 320, UV absorber 328, UV absorber 3039 (octocrylene), UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, glycidyl 1, 4-butanediol ether, diethyl phthalate, diallyl phthalate, diisobutyl phthalate/di-n-butyl phthalate, bis (2-methoxy) ethyl phthalate, bis (4-methyl-2-pentyl) phthalate, bis (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, bis (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, bis (2-ethylhexyl) phthalate, di-n-octyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene/2, 4-diaminotoluene, 2, 4-dimethylaniline, 2, 6-dimethylaniline, aminoazotoluene, aminoazobenzene O-methoxyaniline, 4 '-methenyl-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -dimethylbenzidine, 3 '-dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine 4,4 '-diaminodiphenyl sulfide, 4-chloro-o-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4 '-diaminodiphenyl methane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazol-3-one, methyl chloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, melamine, isophoronediamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexamethylenediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azatridecan-2-one, were selected under the following mass spectrometry conditions:
Positive ion mode: GAS 1:60psi, GAS 2:60psi,Curtain gas:40psi, CAD GAS:7, temperature:600 ℃, spray votage:4500V,TOF MS start mass:100Da,TOF MS stop mass:1000Da,TOF MS Accumulation Time:0.25s,TOF MS Declustering Potential:60V,TOF MS DP spread:0V,TOF MS Collision energy:10V,TOF CE spread:0V,TOF MSMS start mass:50Da,TOF MSMS stop mass:1000Da,TOF MSMS Accumulation Time:0.1s,TOF MSMS Declustering Potential:60V,TOF MSMS DP spread:0,TOF MSMS Collision energy:30V,TOF MSMS CE spread 15V;
in one embodiment, the risk substance is selected from: 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, bischlorophenol, o-phenylphenol, dodecylphenol, 4-tert-octylphenol, nonylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, hexafluorobisphenol A, bisphenol E, bisphenol TMC, bisphenol M, bisphenol OPPA, 4 '-dihydroxytetraphenylmethane, UV-24, UV-0, 4' -dihydroxybenzophenone, perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-xylenol, p-xylene, terephthalic acid, pentachloro-phenol, and 1, p-xylene under mass spectrometry conditions:
Negative ion mode: GAS 1:60psi, GAS 2:60psi,Curtain gas:40psi, CAD GAS:4, temperature:450 ℃, spray votage: -4500V,TOF MS start mass:100Da,TOF MS stop mass:1000Da,TOF MS Accumulation Time:0.25s,TOF MS Declustering Potential: -60V,TOF MS DP spread:0V,TOF MS Collision energy: -5v, tof CE spread:0V,TOF MSMS start mass:50Da,TOF MSMS stop mass:1000Da,TOF MSMS Accumulation Time:0.1s,TOF MSMS Declustering Potential: -60V,TOF MSMS DP spread:0,TOF MSMS Collision energy: 30V,TOF MSMS CE spread 15V.
In one embodiment, the mass spectrometry conditions are detected using the following pairs of detection ions:
the above "-" indicates that no suitable daughter ion can be detected.
In one example, in the preparation of the standard solution, a standard stock solution is prepared with water, methanol or tetrahydrofuran as a solvent, and diluted with methanol to prepare a standard working solution in the following concentration range;
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in one embodiment, in the step of preparing the test solution, a test is taken, a migration solution of a food contact material or an extraction solution obtained by solvent extraction of the test is obtained according to the standards of GB 5009.156 and GB 31604.1, and the migration solution or the extraction solution is centrifuged and then a supernatant is taken to obtain the test solution.
In one embodiment, in the step of detecting the liquid chromatography-mass spectrometry, an electrospray ion source is selected, and a TOF MS or IDA scanning mode is adopted.
In one embodiment, in the step of detecting the liquid chromatography-mass spectrometry, the sample volume is 5 μl in the positive ion mode; the sample volume in the negative ion mode was 2. Mu.L.
The invention also provides application of the method in preparing a reagent for screening dangerous substances in food contact materials.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a screening method of 139 risk substances in food contact materials, which is a screening method for simultaneously detecting most risk substances in the food contact materials, wherein part of compounds are risk substances (such as phthalic acid esters and aromatic amines) which are concerned with more, and the other part of compounds are related detection methods established for the first time. The method optimizes chromatographic determination conditions and mass spectrometry determination conditions, has detection limit of each compound of 0.1-400 mug/L, can evaluate risk substances existing in food contact materials more efficiently and comprehensively, provides good technical support for quality control and safety monitoring of the food contact materials and products, and has good innovation and application value.
Drawings
FIG. 1 is an ion chromatogram of standard solution benzoguanamine and cyclodi-badge extraction;
FIG. 2 is an ion chromatogram of an aluminum bottle sample, 20% ethanol migration solution benzomelamine and cyclo-di-bade extraction.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The risk substance of the present invention refers to a substance which is clearly possible in the art to be used in food packaging materials, but which presents a risk of contaminating food or jeopardizing human health, such as "3Ring node" refers to a component having a CAS number of 158163-01-0, "cyclic-di-BADGE" refers to a component having a CAS number of 20583-87-3,
The reagents used in the following examples, unless otherwise specified, are all commercially available; the methods used in the examples below, unless otherwise specified, are all conventional.
Example 1
A method of screening for risk materials in a food contact material, the method comprising the steps of:
(1) Preparing standard solution
Preparation of individual standard stock solutions: taking each risk substance as a reference substance, respectively weighing about 10mg of the reference substance in a 10mL volumetric flask, dissolving the reference substance in water, methanol or tetrahydrofuran according to the dissolution property of the compound, then fixing the volume to a scale, shaking uniformly, preparing a standard stock solution, and storing at-20 ℃. The standard working solution was prepared by dilution with methanol.
The standard working fluids are divided into two groups, and are detected in a positive ion mode or a negative ion mode respectively.
Wherein the following risk species are detected in positive ion mode: bisphenol A diglycidyl ether, bisphenol A (2, 3-dihydroxypropyl) glycidyl ether, bisphenol A (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether, bisphenol A bis (2, 3-dihydroxypropyl) ether, bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F diglycidyl ether, bisphenol F bis (3-chloro-2-hydroxypropyl) ether, bisphenol F bis (2, 3-dihydroxypropyl) ether, cyclo-di-BADGE, 3ring NOGE, 4ring NOGE, 5ring NOGE, 6ring NOGE, dimethyl phthalate, imazalil, thiabendazole, cyproconazole, propiconazole, tebuconazole, and the like imidacloprid, carbendazim, iodopropynyl butylcarbamate, benzomelamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane 1, 2-dicarboxylate, tributyl acetylcitrate, trimethylol propane trimethacrylate, antioxidant 1098, antioxidant TH-1790, UV absorber 320, UV absorber 328, UV absorber 3039 (octocrylene), UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, glycidyl 1, 4-butanediol ether, diethyl phthalate, diallyl phthalate, diisobutyl phthalate/di-n-butyl phthalate, bis (2-methoxy) ethyl phthalate, bis (4-methyl-2-pentyl) phthalate, bis (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, bis (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, bis (2-ethylhexyl) phthalate, di-n-octyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene/2, 4-diaminotoluene, 2, 4-dimethylaniline, 2, 6-dimethylaniline, aminoazotoluene, aminoazobenzene O-methoxyaniline, 4 '-methenyl-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -dimethylbenzidine, 3 '-dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine 4,4 '-diaminodiphenyl sulfide, 4-chloro-o-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4 '-diaminodiphenyl methane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazol-3-one, methyl chloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, melamine, isophoronediamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexamethylenediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azatridecan-2-one;
The following substances were detected in negative ion mode: 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, dichlorophenol, o-phenylphenol, dodecylphenol, 4-tert-octylphenol, nonylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, hexafluorobisphenol A, bisphenol E, bisphenol TMC, bisphenol M, bisphenol OPPA, 4 '-dihydroxytetraphenylmethane, UV-24, UV-0, 4' -dihydroxybenzophenone, perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-xylenol, p-xylene, 1-xylene, and pentachlorophenol.
The mass spectrometry conditions for positive ion mode were: GAS 1:60psi, GAS 2:60psi,Curtain gas:40psi, CAD GAS:7, temperature:600 ℃, spray votage:4500V,TOF MS start mass:100Da,TOF MS stop mass:1000Da,TOF MS Accumulation Time:0.25s,TOF MS Declustering Potential:60V,TOF MS DP spread:0V,TOF MS Collision energy:10V,TOF CE spread:0V,TOF MSMS start mass:50Da,TOF MSMS stop mass:1000Da,TOF MSMS Accumulation Time:0.1s,TOF MSMS Declustering Potential:60V,TOF MSMS DP spread:0,TOF MSMS Collision energy:30V,TOF MSMS CE spread 15V;
The mass spectrometry conditions of the negative ion mode were: GAS 1:60psi, GAS 2:60psi,Curtain gas:40psi, CAD GAS:4, temperature:450 ℃, spray votage: -4500V,TOF MS start mass:100Da,TOF MS stop mass:1000Da,TOF MS Accumulation Time:0.25s,TOF MS Declustering Potential: -60V,TOF MS DP spread:0V,TOF MS Collision energy: -5v, tof CE spread:0V,TOF MSMS start mass:50Da,TOF MSMS stop mass:1000Da,TOF MSMS Accumulation Time:0.1s,TOF MSMS Declustering Potential: -60V,TOF MSMS DP spread:0,TOF MSMS Collision energy: 30V,TOF MSMS CE spread 15V.
(2) Preparation of test solutions
1) Four paper pipette samples: the paper pipette sample was run at S/V=6dm 2 The paper straw material was cut in the ratio of/L, the area of which was designated as S, and immersed in a 50% (V: V) ethanol aqueous solution having a volume of V at 70℃for 2 hours. Diluting the soaking solution with acetic acid acidified methanol water solution, purifying with ethylenediamine-N-propyl dispersed solid phase extraction material, centrifuging, and collecting supernatant as sample solution. A blank control solution was prepared simultaneously.
2) A pop can sample and an aluminum bottle sample, the pop can sample was prepared with 10% ethanol (V: v) soaking the water solution at 100 ℃ for 2 hours; soaking the aluminum bottle sample in 20% ethanol (V: V) water solution at 40deg.C for 10 days; and (3) after the soaking solution returns to room temperature, centrifuging, and taking the supernatant as a sample solution. A blank control solution was prepared simultaneously.
3) White masterbatch sample: weighing 0.5012g of crushed white master batch sample in a triangular flask with a plug, adding 20mL of normal hexane, ultrasonically extracting for 30min, filtering, repeatedly extracting residues for 1 time by using 20mL of normal hexane, mixing filtrates in a 50mL volumetric flask, fixing the volume to a scale by using normal hexane, uniformly mixing, centrifuging an extracting solution, and taking a supernatant as a sample solution; a blank control solution was prepared simultaneously.
(3) Standard solution high performance liquid chromatography-quadrupole time-of-flight mass spectrometer detection
And (3) detecting the standard working solution on the machine according to the parameter conditions of the different cation modes and the anion modes and the detection conditions described below to obtain the original data.
Chromatographic column: hypersil GOLD TM ，100mm×0.4mm，3μm；
Mobile phase 1: a: according to 0.2mL formic acid: 1L of water is prepared, B: according to 0.156g of ammonium acetate: 0.2mL formic acid: 2mL of water: 200mL of isopropanol: 800mL of methanol is prepared;
mobile phase 2: a: according to 0.2mL formic acid: 1L of water is prepared, B: according to 0.2mL formic acid: 1L of acetonitrile;
mobile phase combination 3: a: according to 0.1mL of ammonia: 1L of water is prepared, B: according to 0.1mL of ammonia: 1L of acetonitrile;
elution procedure 1:0min,0.3mL/min,5% B;3.00min,0.3mL/min,5% B;15.00min,0.55mL/min,95% B;23.00min,0.55mL/min,95% B;24.00min,0.55mL/min,5% B;27.00min,0.55mL/min,5% B;
Elution procedure 2:0min,0.4mL/min,5% B;3.00min,0.4mL/min,5% B;15.00min,0.5mL/min,95% B;21.00min,0.5mL/min,95% B;22.00min,0.5mL/min,5% B;25.00min,0.5mL/min,5% B.
In the above elution procedure, both the flow rate and the mobile phase ratio are linearly graded.
TABLE 1.139 detection conditions for Compounds
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(4) Drawing a standard curve
And (3) referring to the detection conditions, sequentially detecting the concentration gradient standard solution from low concentration to high concentration, drawing a standard curve by taking the concentration of the chemical component to be detected as an abscissa and the peak area of the chemical component to be detected as an ordinate, wherein the standard curve of each compound is shown in Table 2. The detection limit of each compound is calculated by the signal-to-noise ratio of the lowest concentration point, and the concentration when S/N is more than or equal to 3 is the instrument detection limit of the compound.
Table 2.139 standard curve, linear range and detection limit for compounds
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(5) High performance liquid chromatography-quadrupole time-of-flight mass spectrometer detection of sample solution
And (3) detecting the sample solution by referring to the detection conditions, extracting and qualitatively treating chromatographic peaks of the obtained raw data according to the combination parameters of table 1 by using instrument software, and judging whether the sample solution contains the to-be-detected object.
(6) Screening results
Four paper pipette samples: methyl isothiazolinone, 1, 2-benzisothiazol-3-one and methyl chloroisothiazolinone are detected in the sample solutions obtained from four paper pipette samples.
A pop can sample and an aluminum bottle sample: detecting benzomelamine, melamine and bisphenol A-bis (2, 3-dihydroxypropyl) ether in a sample solution obtained from a pop can sample; detecting benzomelamine, cyclo-di-BADGE, bisphenol a- (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol a-bis (2, 3-dihydroxypropyl) ether, bisphenol a- (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether in a sample solution obtained from an aluminum bottle sample;
white masterbatch sample: detecting benzophenone-12 in the sample solution obtained from the white masterbatch;
and detecting benzomelamine and cyclo-di-BADG in a sample solution obtained from an aluminum bottle sample in the screening result, wherein the chromatograms of the benzomelamine and cyclo-di-BADG are shown in figures 1-2 respectively.
Example 2
And (5) optimizing detection conditions.
1. Ion pair selection
This example compares the response intensity of different ionization modes for each compound, baseline noise, isotope peak selection with higher signal-to-noise ratio.
The following examples illustrate: dibenzoate (P) The ketone-6, UV-0,4,4-dihydroxybenzophenone can have either a positive or negative ionization mode, and the benzophenone-6 can simultaneously form [ M+H ]] + And [ M+NH ] 4 ] + Excimer ion, but benzophenone-6 [ M+NH ] under chromatographic condition 1 4 ] + Has the highest chromatographic signal-to-noise ratio, and the [ M-H ] of the UV-0, 4-dihydroxybenzophenone under the chromatographic condition 3] - With the highest chromatographic signal-to-noise ratio;
cyclic-di-badges can form [ M+H ] simultaneously] + And [ M+NH ] 4 ] + Excimer ion, but at chromatographic condition 1 [ M+NH ] 4 ] + With the highest chromatographic signal-to-noise ratio;
the 2,4, 6-trichlorophenol has both 196.9 and 194.9 isotope peaks, but the 196.9 isotope peak has higher chromatographic signal-to-noise ratio.
In this example, the excimer ions and their daughter ions in table 1 were selected as target ions and ion fragments for screening after each compound was relatively preferable.
2. Gas quantity selection
The effect of different CAD gases on the signal to noise ratio of the compound is compared, for example, when CAD gas is set at 4psi, the signal to noise ratio of terephthalic acid and cyclohexanedicarboxylic acid is increased by a factor of 5 and the signal to noise ratio of 4-tert-octylphenol is increased by a factor of one. The signal to noise ratio of other compounds is less affected.
This example compares the effect of selecting different GAS flows on compound response, with GAS flow optimizations ranging from 45psi, 50psi, 55psi, 60psi, 65 psi. In general, the response of some compounds increased with increasing gas flow, with the 60psi and 65psi gap not being evident. Some of the compounds are insensitive to changes in gas flow. Terephthalic acid, cyclohexanedicarboxylic acid, dichlorophenol are sensitive to gas flow changes, with 45psi and 60psi response differences exceeding 100%,200%,50%.
Therefore, comprehensively considering that the GAS1 is 60psi, the GAS 2 is 60psi and the CAD GAS is 7, the characteristics of all the compounds can be considered, and a better response value can be obtained.
3. Vaporization temperature selection
This example compares the effect of selecting different vaporization temperatures on compound response. The temperature optimization ranges from 450 ℃, 500 ℃, 550 ℃ and 600 ℃. For positive ion mode, a vaporization temperature of 600 ℃ may result in a higher response for most compounds. For negative ion mode, perfluorinated compounds are sensitive to temperature changes, higher temperatures can significantly decrease the compound response, and other compounds have less response change between 500 ℃ and 600 ℃.
Therefore, comprehensively considering, the gasification temperature is set to be 500-600, and the characteristics of all the compounds can be considered, so that a better response value can be obtained.
4. Mobile phase selection
For positive ion mode, most compounds have a certain response in both mobile phase combinations, and the mobile phase combination selected in example 1 of the present invention is a result of comparing the signal to noise ratio and linear range of each compound in different mobile combinations, and selecting preferentially.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (7)

1. A method of screening for risk materials in a food contact material comprising the steps of:
preparing a standard solution: preparing a reference substance of the risk substance by using a solvent to prepare a standard working solution; the risk substance is selected from: bisphenol A-diglycidyl ether, bisphenol A- (2, 3-dihydroxypropyl) glycidyl ether, bisphenol A- (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether, bisphenol A-bis (3-chloro-2-hydroxypropyl) ether, bisphenol A- (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F-diglycidyl ether, bisphenol F-bis (3-chloro-2-hydroxypropyl) ether, bisphenol F-bis (2, 3-dihydroxypropyl) ether, 3Ring NOGE,4Ring NOGE,5Ring NOGE,6Ring NOGE,cyclo-di-BADGE, dimethyl phthalate, diethyl phthalate, diallyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, dibenzyl phthalate, di (2-butoxy) diethyl phthalate, di (2-ethyl) 2, 6-n-butyl phthalate, di-2-n-butyl phthalate, di-2-butyl phthalate, di-n-butyl phthalate, di-2-n-butyl phthalate, 2, 4-dimethylaniline, 2, 6-dimethylaniline, o-aminoazotoluene, p-aminoazobenzene, o-methoxyaniline, 4 '-methylene-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -dimethylbenzidine, 3 '-dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4 '-diaminodiphenyl sulfide, 4-chloro-o-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4 '-diaminodiphenyl methane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), imazalil, thiabendazole, methylisothiazolinone, 1, 2-benzisothiazol-3-one, methyl chloroisothiazolinone, cyproconazole, propiconazole, tebuconazole, imidacloprid, carbendazim, 2-octyl-4-isothiazolin-3-one, iodopropynyl butylcarbamate, melamine, benzomelamine, caprolactam, isophoronediamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexamethylenediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, diethylhexyl adipate, cyclohexane 1, 2-dicarboxylic acid diisononyl ester, acetyl tributyl citrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, UV absorber 320, UV absorber 328, UV absorber 3039, UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, azacyclotridin-2-one, 1, 4-butanediol glycidyl ether, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, dichlorophenol, o-phenylphenol, dodecylphenol, 4-tert-octylphenol, nonylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, hexafluorobisphenol A, bisphenol E, bisphenol TMC, bisphenol M, bisphenol OPPA,4 '-dihydroxytetraphenyl methane, UV-24, UV-0,4,4' -dihydroxybenzophenone, perfluorobutyric acid, perfluorovaleric acid, perfluorocaproic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-chlorom-xylenol, pentachlorophenol, terephthalic acid and 1, 4-cyclohexanedicarboxylic acid;
Preparing a test solution: taking a contact material as a test sample, and performing pretreatment to obtain a test sample solution;
and (3) liquid chromatography-mass spectrometry detection: detecting the standard working solution and the sample solution by adopting a high performance liquid chromatography-quadrupole flight time mass spectrometer respectively;
and (3) result judgment: comparing the detection result of the sample solution with the detection result of the standard working solution to obtain a screening result of the risk substance;
when the risk substance is selected from: bisphenol A diglycidyl ether, bisphenol A (2, 3-dihydroxypropyl) glycidyl ether, bisphenol A (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether, bisphenol A bis (3-chloro-2-hydroxypropyl) ether, bisphenol A- (3-chloro-2-hydroxypropyl) glycidyl ether bisphenol F-diglycidyl ether, bisphenol F-bis (3-chloro-2-hydroxypropyl) ether, bisphenol F-bis (2, 3-dihydroxypropyl) ether, cyclo-di-BADGE, 3ring NOGE, 4ring NOGE, 5ring NOGE, 6ring NOGE, dimethyl phthalate, imazalil thiabendazole, cyproconazole, propiconazole, tebuconazole, imidacloprid, carbendazim, iodopropynyl butylcarbamate, benzomelamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane 1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, ultraviolet absorber 320, ultraviolet absorber 328, ultraviolet absorber 3039, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, 1, 4-butanediol glycidyl ether;
The following first chromatographic assay conditions were selected:
chromatographic column: hypersil GOLD TM ，100mm×4.0mm，3μm；
Mobile phase 1: a: according to 0.2mL formic acid: 1L of water is prepared, B: according to 0.156g of ammonium acetate: 0.2mL formic acid: 2mL of water: 200mL of isopropanol: 800mL of methanol is prepared;
elution procedure 1: the ratio of the flow rate to the mobile phase B is adjusted according to the following time points, and the ratio of the flow rate to the mobile phase B is in linear gradient change between the two time points;
when the risk substance is selected from: diethyl phthalate, diallyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, di-n-octyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene, and the like 2, 4-diaminotoluene, 2, 4-dimethylaniline, 2, 6-dimethylaniline, o-aminoazotoluene, p-aminoazobenzene, o-methoxyaniline, 4' -methenyl-bis- (2-chloroaniline), 3' -dimethyl-4, 4' -diaminodiphenylmethane, 3' -dimethylbenzidine, 3' -dimethoxybenzidine 3,3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4' -diaminodiphenyl sulfide, 4-chlorophthalide, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4' -diaminodiphenyl methane, 4,4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazolin-3-one, methylchloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, melamine, isophoronediamine, 4' -methylenebis (2-methylcyclohexylamine), 1, 6-hexamethylenediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, di (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azatridecan-2-one;
The following second chromatographic assay conditions were selected:
chromatographic column: hypersil GOLD TM ，100mm×4.0mm，3μm；
Mobile phase 2: a: according to 0.2mL formic acid: 1L of water is prepared, B: according to 0.2mL formic acid: 1L of acetonitrile;
the elution procedure 1;
when the risk substance is selected from: 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, dichlorophenol, o-phenylphenol, dodecylphenol, 4-tert-octylphenol, nonylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, hexafluorobisphenol A, bisphenol E, bisphenol TMC, bisphenol M, bisphenol OPPA, 4 '-dihydroxytetraphenylmethane, UV-24, UV-0, 4' -dihydroxybenzophenone, perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-xylenol, p-xylene, 1-xylene, pentachlorophenol, pentachloro acid;
the following third chromatography assay conditions were selected:
Chromatographic column: hypersil GOLD TM ，100mm×4.0mm，3μm；
Mobile phase 3: a: according to 0.1mL of ammonia: 1L of water is prepared, B: according to 0.1mL of ammonia: 1L of acetonitrile;
elution procedure 2: the ratio of the flow rate to the mobile phase B is adjusted according to the following time points, and the ratio of the flow rate to the mobile phase B is in linear gradient change between the two time points;
in the liquid chromatography-mass spectrometry detection step, the following detection conditions are adopted: CAD GAS is set to 4-7psi, GAS1 and GAS2 are set to 45-65psi, and the temperature is set to 500-600 ℃;
when the risk substance is selected from: bisphenol A diglycidyl ether, bisphenol A (2, 3-dihydroxypropyl) glycidyl ether, bisphenol A (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether, bisphenol A bis (3-chloro-2-hydroxypropyl) ether, bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol F diglycidyl ether bisphenol F-bis (3-chloro-2-hydroxypropyl) ether, bisphenol F-bis (2, 3-dihydroxypropyl) ether, cyclic-di-BADGE, 3ring NOGE, 4ring NOGE, 5ring NOGE, 6ring NOGE, dimethyl phthalate, imazalil, thiabendazole, cyproconazole, propiconazole, tebuconazole, imidacloprid, carbendazim, and iodopropynyl butylcarbamate, benzomelamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane 1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, UV absorber 320, UV absorber 328, UV absorber 3039, UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, 1, 4-butanediol glycidyl ether, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di (2-methoxy) ethyl phthalate, bis (4-methyl-2-pentyl) phthalate, bis (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, bis (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, bis (2-ethylhexyl) phthalate, di-n-octyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene, 2, 4-dimethylaniline, 2, 6-dimethylaniline, aminoazotoluene, p-aminoazobenzene, methoxyaniline, 4,4 '-methenyl-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -dimethylbenzidine, 3 '-dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4 '-diaminodiphenyl sulfide 4-chloro-o-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4 '-diaminodiphenylmethane 4,4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazol-3-one, methylchloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, melamine, isophoronediamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexamethylenediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, di (2-hydroxypropyl) amine, triisopropanolamine, aziridec-2-one;
The following mass spectrometry conditions were selected:
positive ion mode: GAS1:60psi, GAS2:60psi,Curtain gas:40psi, CAD GAS:7, temperature:600 ℃, spray votage:4500V,TOF MS start mass:100Da,TOF MS stop mass:1000Da,TOF MS Accumulation Time:0.25s,TOF MSDeclustering Potential:60V,TOF MSDP spread:0V,TOF MS Collision energy:10V,TOF CE spread:0V,TOF MSMS start mass:50Da,TOF MSMS stop mass:1000Da,TOF MSMS Accumulation Time:0.1s,TOF MSMSDeclustering Potential:60V,TOF MSMSDP spread:0,TOF MSMS Collision energy:30V,TOF MSMS CE spread 15V;
when the risk substance is selected from: 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, dichlorophenol, o-phenylphenol, dodecylphenol, 4-tert-octylphenol, nonylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, hexafluorobisphenol A, bisphenol E, bisphenol TMC, bisphenol M, bisphenol OPPA, 4 '-dihydroxytetraphenylmethane, UV-24, UV-0, 4' -dihydroxybenzophenone, perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, p-xylenol, p-xylene, 1-xylene, pentachlorophenol, pentachloro acid;
The following mass spectrometry conditions were selected:
negative ion mode: GAS1:60psi, GAS2:60psi,Curtain gas:40psi, CAD GAS:4, temperature:450 ℃, spray votage: -4500V,TOF MS start mass:100Da,TOF MS stop mass:1000Da,TOF MS Accumulation Time:0.25s,TOF MSDeclustering Potential: -60V,TOF MSDP spread:0V,TOF MS Collision energy: -5v, tof CE spread:0V,TOF MSMS start mass:50Da,TOF MSMS stop mass:1000Da,TOF MSMS Accumulation Time:0.1s,TOF MSMSDeclustering Potential: -60V,TOF MSMSDP spread:0,TOF MSMS Collision energy: 30V,TOF MSMS CE spread15V.
2. The method of screening for risk materials in food contact materials according to claim 1, wherein the mass spectrometry conditions are detected using the following pairs of detection ions:
3. the method of screening for risk substances in a food contact material according to claim 1, wherein in preparing the standard solution, a standard stock solution is prepared using water, methanol or tetrahydrofuran as a solvent, and diluted with methanol, and a standard working solution is prepared in the following concentration range;
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4. The method for screening risk substances in a food contact material according to claim 1, wherein in the step of preparing a test solution, a test solution is obtained, a migration solution of the food contact material or an extraction solution obtained by solvent extraction of the test solution is obtained according to the standards GB 5009.156 and GB 31604.1, and the migration solution or the extraction solution is centrifuged and a supernatant is obtained to obtain the test solution.
5. The method of claim 1, wherein in the step of detecting by liquid chromatography-mass spectrometry, electrospray ion source is selected and either TOF MS or IDA scanning mode is used.
6. The method of claim 1, wherein in the step of detecting by liquid chromatography-mass spectrometry, the sample volume is 5 μl in positive ion mode; the sample volume in the negative ion mode was 2. Mu.L.
7. Use of the method of any one of claims 1-6 for screening for risk substances in food contact materials.
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CN115902020A (en) * 2022-11-24 2023-04-04 华熙生物科技股份有限公司 Method for detecting polyhydric alcohol
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108344822A (en) * 2018-02-11 2018-07-31 张宪臣 The remaining analysis method of several additives in a kind of measurement food contact plastic products
JP2018203654A (en) * 2017-06-01 2018-12-27 三菱ケミカル株式会社 Method for producing bisphenol compound, and method for producing polycarbonate resin
CN110082437A (en) * 2019-03-27 2019-08-02 中国检验检疫科学研究院 The method for detecting bisphenol compound
CN110715999A (en) * 2019-11-08 2020-01-21 中国检验检疫科学研究院 High-throughput screening method for 200 chemical risk substances in toy
CN112986416A (en) * 2021-02-03 2021-06-18 暨南大学 Multi-component large-flux detection method for plastic additive in atmospheric particulates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060183238A1 (en) * 2005-02-09 2006-08-17 Applera Corporation Amine-containing compound analysis methods

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018203654A (en) * 2017-06-01 2018-12-27 三菱ケミカル株式会社 Method for producing bisphenol compound, and method for producing polycarbonate resin
CN108344822A (en) * 2018-02-11 2018-07-31 张宪臣 The remaining analysis method of several additives in a kind of measurement food contact plastic products
CN110082437A (en) * 2019-03-27 2019-08-02 中国检验检疫科学研究院 The method for detecting bisphenol compound
CN110715999A (en) * 2019-11-08 2020-01-21 中国检验检疫科学研究院 High-throughput screening method for 200 chemical risk substances in toy
CN112986416A (en) * 2021-02-03 2021-06-18 暨南大学 Multi-component large-flux detection method for plastic additive in atmospheric particulates

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Analytical strategies for organic food packaging contaminants;Yovana Sanchis Vicent Yus`a Clara Coscoll`;Journal of Chromaiography A;20171231;1-71 *
液相色谱-串联质谱法测定 食品接触材料中28 种初级芳香胺的迁移量;李全忠等;分析化学( FENXI HUAXUE) 研究报告;20130131;第41卷(第1期);25-30 *
超高效液相色谱法同时测定食品塑料包装材料 中的紫外吸收剂和抗氧化剂;陈立伟等;分析测试学报;20160229;第35卷(第2期);206-212 *

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