CN114755316A - 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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CN114755316A
CN114755316A CN202210196209.4A CN202210196209A CN114755316A CN 114755316 A CN114755316 A CN 114755316A CN 202210196209 A CN202210196209 A CN 202210196209A CN 114755316 A CN114755316 A CN 114755316A
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phthalate
acid
bisphenol
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butyl
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CN114755316B (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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Abstract

The invention relates to a method for screening dangerous substances in food contact materials and application. The method comprises the following steps: preparation of standard solutions: preparing a reference substance of a risk substance, wherein the risk substance is selected from 139 substances such as bisphenol A-diglycidyl ether and the like; preparing a test solution: taking the contact material as a test sample, and carrying out pretreatment to obtain a test sample solution; and (3) liquid chromatography-mass spectrometry detection: respectively detecting the standard working solution and the test solution by adopting a high performance liquid chromatography-quadrupole time-of-flight mass spectrometer; and (4) judging a result: and comparing the detection result of the test solution with the detection result of the standard working solution to obtain a screening result of the risk substances. The method optimizes chromatographic determination conditions and mass spectrometry determination conditions, has detection limit of each compound between 0.1-400 mug/L, can evaluate risk substances 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 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
Food contact materials are also known as indirect food additives because of the close contact with the food and the possible migration of ingredients into the contents that affect food safety. The exposure risk of the risk substances in the food contact material to the human body is represented by three characteristics of passivity, unavailability and long-term property, and the trace amount of the risk substances can cause huge potential safety hazards to the health and the safety of consumers. Food safety events caused by food contact materials have been frequent in recent years, such as: bisphenol a events in baby bottles, phthalate plasticizer events in plastic food packaging products, and the like, all sound a bell for safe use of food contact materials. Many risk substances in the food contact material are not identified, and most of the current detection methods for the safety risk substances of the food contact material only aim at a single substance or a class of substances, and the technical research of simultaneously screening multiple types of risk substances is less considered, so that the protection of consumers is insufficient.
The liquid chromatogram-quadrupole time-of-flight mass spectrometer is a mass spectrometry analysis technology which uses a liquid chromatogram as a separation system, an electrospray or normal pressure chemical ionization source as an ionization mode, and quadrupole cascade flight time as a mass analyzer. The method has the advantages of multi-dimensional analysis parameter setting, high sensitivity, high resolution and high acquisition speed, and endows the method with extremely high chemical component acquisition and analysis capability (acquiring dozens to thousands of chemical components by one injection), combines with huge data processing function and statistical analysis function of software, and is widely applied to screening of pesticide residues, veterinary drug residues and illegal additives in food, screening of soluble substances and extractables, unintended additives and substances with high concern in food/drug packaging, screening of substances for forbidden use in cosmetics, identification of chemical components in traditional Chinese medicines, drug metabolism, proteomics and the like, and detection and research directions.
Therefore, a method for comprehensively screening dangerous substances in food contact materials based on liquid chromatography-quadrupole time-of-flight mass spectrometry is urgently needed to be provided.
Disclosure of Invention
In view of the above, there is a need to provide a method for screening food contact materials for hazardous materials.
A method of screening for hazardous materials in food contact materials comprising the steps of:
preparation of standard solutions: preparing a reference substance of the risk substance by using a solvent to prepare a standard working solution; the risk substances include: 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, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di-n-octyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene, 2, 4-dimethylaniline, 2, 6-dimethylaniline, o-aminoazotoluene, p-aminoazobenzene, o-methoxyaniline, 4,4 '-methine-bis- (2-chloroaniline), 3,3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3,3' -dimethylbenzidine, 3,3 '-dimethoxybenzidine, 3,3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4,4 '-diaminodiphenyl sulfide, 4-chloroo-toluidine, 4,4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4,4 '-diaminodiphenylmethane, 4,4' -methylenebis (3-chloro-2, 6-diethylaniline), imazalil, thiabendazole, methylisothiazolinone, 1, 2-benzisothiazol-3-one, methylchloroisothiazolinone, cyproconazole, propiconazole, tebuconazole, imidacloprid, carbendazim, 2-octyl-4-isothiazolin-3-one, iodopropynyl butylcarbamate, melamine, benzoguanamine, caprolactam, isophoronediamine, 4,4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexanediamine, 11-aminoundecanoic acid, 4,4' -diaminodicyclohexylmethane, N, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, diethylhexyladipate, cyclohexane 1, 2-dicarboxylic acid diisononyl ester, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, ultraviolet absorbent 320, ultraviolet absorbent 328, ultraviolet absorbent 3039, UV-9, benzophenone-12, benzophenone-6, 2- (dimethoxy) ethyl methacrylate, azacyclotridecane-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, 4,4' -dihydroxytetraphenylmethane, UV-24, UV-0, 4,4 '-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, parachlorometaxylenol, pentachlorophenol, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid, 4,4' -dihydroxytetraphenylmethane, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, parachlorometaxylenol, 4-chloro-3-cresol, terephthalic acid and 1, 4-cyclohexanedicarboxylic acid;
preparing a test solution: taking the contact material as a test sample, and carrying out pretreatment to obtain a test sample solution;
and (3) liquid chromatography-mass spectrometry detection: respectively detecting the risk substances by adopting a high performance liquid chromatography-quadrupole time-of-flight mass spectrometer for the standard working solution and the test solution;
and (4) judging a result: and comparing the detection result of the test solution with the detection result of the standard working solution to obtain a screening result of the risk substances.
The invention relates to a screening method for 139 risk substances in food contact materials, which is a screening method for simultaneously detecting the most risk substances in the currently known food contact materials, wherein part of compounds are risk substances (such as phthalate esters and aromatic amines) which are concerned more, and part of compounds are risk substances (such as Cyclo-di-BADGE, benzoguanamine and the like) for establishing 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, benzoguanamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane 1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, an antioxidant 1098, an antioxidant TH-1790, an ultraviolet absorbent 320, an ultraviolet absorbent 328, an ultraviolet absorbent 3039 (octocrylene), UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate and 1, 4-butanediol glycidyl ether;
the following first chromatographic measurement conditions were selected:
a chromatographic column: hypersil GOLDTM，100mm×0.4mm，3μm；
Mobile phase 1: a: formic acid was added as 0.2 mL: 1L of water, B: according to 0.156g ammonium acetate: 0.2mL of formic acid: 2mL of water: 200mL of isopropanol: preparing 800mL of methanol;
elution procedure 1: adjusting the flow rate and the proportion of the mobile phase B according to the following time points, wherein the flow rate and the proportion of the mobile phase B are both in linear gradient change between the two time points;
Figure BDA0003525841940000031
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, di-n-butyl phthalate, di (2-methoxy) ethyl phthalate, di (2-butoxy) ethyl phthalate, di (2-cyclohexyl) phthalate, di (2-ethylhexyl) phthalate, di (2-n-octyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene/2, 4-diaminotoluene, 2, 4-dimethylaniline, 2, 6-methylaniline, di-n-methylaniline, di-butyl phthalate, di (2-butyl) ethyl phthalate, di-benzyl phthalate, di (2-butyl) ethyl phthalate, di (2-butyl) ethyl phthalate, di-butyl-phthalate, di (2-butyl) ethyl phthalate, di-butyl-phthalate, di-butyl-phthalate, di-butyl-phthalate, di-butyl-ethyl phthalate, di-butyl-phthalate, di-butyl-phthalate, di-ethyl phthalate, di-butyl-phthalate, di-butyl-ethyl phthalate, di-butyl-phthalate, O-aminoazotoluene, p-aminoazobenzene, o-methoxyaniline, 4 '-methine-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-chloroo-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4 '-diaminodiphenylmethane, 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-hexanediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azacyclotridecan-2-one;
the following second chromatographic measurement conditions were selected:
a chromatographic column: hypersil GOLDTM，100mm×0.4mm，3μm；
Mobile phase 2: a: formic acid was added as 0.2 mL: 1L of water, B: formic acid was added as 0.2 mL: 1L of acetonitrile is prepared;
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, dichlorophenol, orthophenylphenol, 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, parachlorometaxylenol, pentachlorophenol, terephthalic acid 1, 4-cyclohexanedicarboxylic acid;
the following third chromatographic measurement conditions were selected:
and (3) chromatographic column: hypersil GOLDTM，100mm×0.4mm，3μm；
Mobile phase 3: a: ammonia was added as 0.1 mL: 1L of water, B: ammonia was added as 0.1 mL: 1L of acetonitrile is prepared;
elution procedure 2: adjusting the flow rate and the proportion of the mobile phase B according to the following time points, wherein the flow rate and the proportion of the mobile phase B are changed in a linear gradient manner between the two time points;
Figure BDA0003525841940000041
the flow combination adopted by the invention is the result of comparing the signal-to-noise ratio and the linear range of each compound in different flow combinations, and preferably selecting. Specifically, the [ M + NH ] can be increased by selecting the first chromatographic conditions for the risk substance corresponding to the first chromatographic conditions4]+The fraction [ M + H ] which is the signal-to-noise ratio of the compounds in the main ionization mode]+The compounds also have a higher signal-to-noise ratio under the first chromatographic conditions; for most aromatic amine compounds, the second chromatographic determination condition can provide higher signal-to-noise ratio; the first chromatographic condition and the second chromatographic condition can form better complementary action on the compound in the positive ionization mode, so that the method can cover moreA number of risk substances; the third chromatographic conditions may be compatible with the negatively ionized compounds mentioned in the methods. The addition of ammonium acetate salt in the mobile phase reduced the response (signal to noise ratio) of some of the compounds, so ammonium acetate was not added in the chromatographic conditions.
In one embodiment, the following detection conditions are adopted in the LC-MS detection step: CAD GAS was set at 4-7psi, GAS1 and GAS2 were both set at 45-65psi, and the temperature was set at 500-600 ℃.
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, benzoguanamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane-1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, ultraviolet absorbent 320, ultraviolet absorbent 328, ultraviolet absorbent 3039 (octocrylene), UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, 1, 4-butanediol glycidyl ether, 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 '-methine-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 2, 6' -diaminodiphenylmethane, 3,3' -dimethylbenzidine, 3' -dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4' -diaminodiphenyl sulfide, 4-chloroo-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine ether, 4-aminobiphenyl, 4' -diaminodiphenylmethane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazol-3-one, methylchloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, water-soluble salts thereof, and the like, Melamine, isophorone diamine, 4 '-methylene bis (2-methylcyclohexylamine), 1, 6-hexamethylene diamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azacyclotridecan-2-one, using the following mass spectrometric conditions:
positive ion mode: and the 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 patent: 60V, TOF MS DP spread: 0V, TOF MS condensation energy: 10V, TOF CE spread: 0V, TOF MSMS start mass: 50Da, TOF MSMS stop mass: 1000Da, TOF MSMS Accumulation Time: 0.1s, TOF MSMS Classification Potential: 60V, TOF MSMS DP spread: 0, TOF MSMS fusion 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, dichlorophenol, orthophenylphenol, 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, parachlorometaxylenol, pentachlorophenol, terephthalic acid and 1, 4-cyclohexanedicarboxylic acid, under the following mass spectrometric conditions:
negative ion mode: and the 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 Classification Potential: -60V, TOF MS DP spread: 0V, TOF MS condensation energy: -5V, TOF CE spread: 0V, TOF MSMS start mass: 50Da, TOF MSMS stop mass: 1000Da, TOF MSMS Accumulation Time: 0.1s, TOF MSMS Classification Potential: -60V, TOF MSMS DP spread: 0, TOF MSMS fusion energy: 30V, TOF MSMS CE spread 15V.
In one embodiment, the mass spectrometry conditions are such that the following pairs of detector ions are used for detection:
Figure BDA0003525841940000061
Figure BDA0003525841940000071
Figure BDA0003525841940000081
Figure BDA0003525841940000091
Figure BDA0003525841940000101
the above "-" indicates that no suitable daughter ion was detectable.
In one embodiment, in the preparation of the standard solution, a standard stock solution is prepared by using water, methanol or tetrahydrofuran as a solvent, and diluted by using methanol to prepare a standard working solution according to the following concentration range;
Figure BDA0003525841940000102
Figure BDA0003525841940000111
Figure BDA0003525841940000121
Figure BDA0003525841940000131
Figure BDA0003525841940000141
in one embodiment, in the step of preparing the sample solution, the sample is taken, a migration liquid of the food contact material or an extract liquid obtained by extracting the sample with a solvent is obtained according to the standards of GB 5009.156 and GB 31604.1, and the supernatant is taken after centrifuging the migration liquid or the extract liquid, which is the sample solution.
In one embodiment, in the step of LC-MS detection, an electrospray ion source is selected, and a TOF MS or IDA scanning mode is adopted.
In one embodiment, in the step of LC-MS detection, the sample injection volume is 5 μ L in positive ion mode; the injection volume in the negative ion mode was 2. mu.L.
The invention also provides the use of the above method in the preparation of a reagent for screening for a substance at risk in a food contact material.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a screening method for 139 risk substances in food contact materials, which is a screening method for simultaneously detecting the most risk substances in the currently known food contact materials, wherein part of compounds are risk substances (such as phthalates and aromatic amines) which are concerned more, and 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 0.1-400 μ g/L for each compound, can evaluate risk substances 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 good innovation and application value.
Drawings
FIG. 1 is a chromatogram of standard solution benzoguanamine and cyclo-di-badge extracted ions;
FIG. 2 is an ion chromatogram of 20% ethanol migration solution benzoguanamine and cyclo-di-badge extraction of an aluminum bottle sample.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The risk substances of the present invention refer to substances which are definitely possible in the art for use in food packaging materials, but which present a risk of contaminating food or endangering human health, e.g. "3 Ring NOGE" refers to a composition with CAS number 158163-01-0, "cyclo-di-BADGE" refers to a composition with CAS number 20583-87-3,
the reagents used in the following examples, unless otherwise specified, are all commercially available; the methods used in the following examples, unless otherwise specified, are all routinely practiced.
Example 1
A method of screening for a hazardous material 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, weighing about 10mg of the reference substance into a 10mL volumetric flask respectively, dissolving the reference substance with water, methanol or tetrahydrofuran according to the dissolution property of the compound, fixing the volume to a scale, shaking up, preparing a standard storage solution, and storing at-20 ℃. The standard working solution was prepared by dilution with methanol.
The standard working solution is divided into two groups, and the detection is carried out in a positive ion mode or a negative ion mode respectively.
Wherein the following risk substances 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, imidacloprid, carbendazim, iodopropynyl butylcarbamate, benzoguanamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane-1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, ultraviolet absorbent 320, ultraviolet absorbent 328, ultraviolet absorbent 3039 (octocrylene), UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, 1, 4-butanediol glycidyl ether, 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 '-methine-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 2, 6' -diaminodiphenylmethane, 3,3' -dimethylbenzidine, 3' -dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4' -diaminodiphenyl sulfide, 4-chloroo-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine ether, 4-aminobiphenyl, 4' -diaminodiphenylmethane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazol-3-one, methylchloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, water-soluble salts thereof, and the like, Melamine, isophorone diamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexanediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azacyclotridecan-2-one;
the following were detected in negative ion mode: 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, dichlorophenol, orthophenylphenol, 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, parachlorometaxylenol, pentachlorophenol, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid.
The mass spectrometry conditions in the positive ion mode were: the 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 patent: 60V, TOF MS DP spread: 0V, TOF MS condensation energy: 10V, TOF CE spread: 0V, TOF MSMS start mass: 50Da, TOF MSMS stop mass: 1000Da, TOF MSMS Accumulation Time: 0.1s, TOF MSMS Classification Potential: 60V, TOF MSMS DP spread: 0, TOF MSMS fusion energy: 30V, TOF MSMS CE spread 15V;
the mass spectrometry conditions in the negative ion mode were: and the 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 patent: -60V, TOF MS DP spread: 0V, TOF MS precision: -5V, TOF CE spread: 0V, TOF MSMS start mass: 50Da, TOF MSMS stop mass: 1000Da, TOF MSMS Accumulation Time: 0.1s, TOF MSMS Classification Potential: 60V, TOF MSMS DP spread: 0, TOF MSMS fusion energy: 30V, TOF MSMS CE spread 15V.
(2) Preparing test solution
1) Four paper pipette samples: the paper pipette sample is measured according to S/V of 6dm2The paper pipette material is cut at the ratio of/L, the area of which is marked as S, and is soaked in 50% (V: V) ethanol aqueous solution with the volume of V for 2 hours at 70 ℃. The soaking solution is diluted by methanol aqueous solution acidified by acetic acid and purified by ethylenediamine-N-propyl dispersed solid phase extraction materialCentrifuging, and taking supernatant as a test solution. A blank control is also prepared.
2) One can sample and one aluminum bottle sample, the can sample was prepared with 10% ethanol (V: v) soaking the water solution for 2 hours at 100 ℃; soaking the aluminum bottle sample in 20% ethanol (V: V) water solution at 40 deg.C for 10 days; and after the soak solution is returned to the room temperature, centrifuging, and taking supernate as a test solution. A blank control solution was also prepared.
3) White color masterbatch sample: weighing 0.5012g of crushed white color master batch sample in a triangular flask with a plug, adding 20mL of n-hexane, performing ultrasonic extraction for 30min, filtering, repeatedly extracting the residue with 20mL of n-hexane for 1 time, combining the filtrates in a 50mL volumetric flask, fixing the volume to a scale with n-hexane, mixing uniformly, taking the extracting solution for centrifugation, and taking the supernatant as a test solution; a blank control solution was also prepared.
(3) Standard solution high performance liquid chromatography-quadrupole time-of-flight mass spectrometer detection
And (3) performing computer detection on the standard working solution according to the parameter conditions of different cation modes and anion modes and the detection conditions to obtain original data.
And (3) chromatographic column: hypersil GOLDTM，100mm×0.4mm，3μm；
Mobile phase 1: a: formic acid was added as 0.2 mL: 1L of water, B: as 0.156g ammonium acetate: 0.2mL of formic acid: 2mL of water: 200mL of isopropanol: preparing 800mL of methanol;
mobile phase 2: a: formic acid was added as 0.2 mL: 1L of water, B: formic acid was added as 0.2 mL: 1L of acetonitrile is prepared;
flow phase combination 3: a: ammonia was added as 0.1 mL: 1L of water, B: ammonia was added as 0.1 mL: 1L of acetonitrile is prepared;
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 flow ratio were linearly graded.
TABLE 1.139 test conditions for the Compounds
Figure BDA0003525841940000171
Figure BDA0003525841940000181
Figure BDA0003525841940000191
Figure BDA0003525841940000201
(4) Drawing a standard curve
And (3) sequentially detecting the concentration gradient standard solution from low concentration to high concentration according to the detection conditions, drawing a standard curve by taking the concentration of the chemical component to be detected as a horizontal ordinate and the peak area of the chemical component to be detected as a vertical coordinate, wherein the standard curve of each compound is shown in a table 2. And calculating the detection limit of each compound by using the signal-to-noise ratio of the lowest concentration point, wherein the concentration when the 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 the Compounds
Figure BDA0003525841940000202
Figure BDA0003525841940000211
Figure BDA0003525841940000221
Figure BDA0003525841940000231
Figure BDA0003525841940000241
(5) High performance liquid chromatography-quadrupole time-of-flight mass spectrometer detection of test sample solution
And (3) detecting the test solution by referring to the detection conditions, performing chromatographic peak extraction and qualitative treatment on the obtained original data according to the combination parameters in the table 1 by using instrument software, and judging whether the test solution contains the substance to be detected.
(6) Results of screening
Four paper pipette samples: methylisothiazolinone, 1, 2-benzisothiazol-3-one and methylchloroisothiazolinone were detected in the test solutions obtained from four paper pipette samples.
One can sample and one aluminum bottle sample: detecting benzoguanamine, melamine and bisphenol A-bis (2, 3-dihydroxypropyl) ether in a test solution obtained from a pop can sample; detecting benzoguanamine, cyclo-di-BADGE, bisphenol A- (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol A-bis (2, 3-dihydroxypropyl) ether and bisphenol A- (3-chloro-2-hydroxypropyl) (2, 3-dihydroxypropyl) ether in a test solution obtained from an aluminum bottle sample;
white color masterbatch sample: detecting benzophenone-12 in a test solution obtained from the white color master batch;
in the screening result, benzoguanamine and cyclo-di-BADG are detected in the test solution obtained from the aluminum bottle sample, and the chromatograms are respectively shown in figures 1-2.
Example 2
And (4) optimizing detection conditions.
1. Ion pair selection
This example compares the response intensity of different ionization modes for each compound, baseline noise, and isotope peak selection with higher signal-to-noise ratio.
The following is illustrative: benzophenone-6, UV-0, 4, 4-dihydroxy benzophenone can have positive ion ionization mode or negative ion ionization mode, and benzophenone-6 can simultaneously form [ M + H]+And [ M + NH ]4]+Excimer ion, but [ M + NH ] of benzophenone-6 under chromatographic conditions 14]+With the highest chromatographic signal-to-noise ratio, [ M-H ] of UV-0, 4-dihydroxybenzophenone under chromatographic condition 3]-Has the highest chromatographic signal-to-noise ratio;
cyclo-di-badge can form [ M + H ] at the same time]+And [ M + NH ]4]+Quasi-molecular ion, but [ M + NH ] at chromatographic condition 14]+Has the highest chromatographic signal-to-noise ratio;
the 2,4, 6-trichlorophenol has isotope peaks of 196.9 and 194.9, but the 196.9 isotope peak has higher chromatographic signal-to-noise ratio.
In this example, after each compound is preferred, the excimer ions and their daughter ions shown in table 1 are selected as the target ions and ion fragments for screening.
2. Gas quantity selection
The effect of different CAD gases on the signal-to-noise ratio of the compounds was compared, for example, the signal-to-noise ratio of terephthalic acid and cyclohexanedicarboxylic acid was increased by a factor of 5 and the signal-to-noise ratio of 4-tert-octylphenol was increased by a factor of two when the CAD gas was set to 4psi compared to 7psi for CAD. The signal to noise ratio for other compounds is less affected.
This example compares the effect of selecting different GAS flows on the compound response, with the GAS1 and GAS2 optimized for flows ranging from 45psi, 50psi, 55psi, 60psi, 65psi, etc. Overall, the response of the partial compounds increased with increasing gas flow, with no significant difference between 60psi and 65 psi. Some compounds are not sensitive to changes in gas flow. Terephthalic acid, cyclohexanedicarboxylic acid, and bischlorophenol are sensitive to gas flow variations, with response differences of 45psi and 60psi exceeding 100%, 200%, and 50%.
Therefore, by taking the combination of GAS1 at 60psi, GAS2 at 60psi and CAD GAS at 7, all compound characteristics can be considered and superior response values can be obtained.
3. Selection of gasification temperature
This example compares the effect of selecting different vaporization temperatures on compound response. The temperature optimization range is from 450 ℃, 500 ℃, 550 ℃ and 600 ℃. For positive ion mode, a vaporization temperature of 600 ℃ gives a higher response for most compounds. For the negative ion mode, the perfluorinated compounds are sensitive to temperature changes, higher temperatures can significantly reduce the response of the compounds, and the response of other compounds is not changed greatly between 500 ℃ and 600 ℃.
Therefore, the gasification temperature is set to 500-.
4. Mobile phase selection
For positive ion mode, most compounds have certain responses in both flow combinations, and the flow combination selected in example 1 of the present invention compares the signal-to-noise ratio, and linear range, of each compound in different flow combinations, with the preferred results.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A method of screening for hazardous material in food contact material, comprising the steps of:
preparation of standard solutions: 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 (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, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di-n-octyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene, 2, 4-dimethylaniline, 2, 6-dimethylaniline, o-aminoazotoluene, p-aminoazobenzene, o-anisidine, 4,4 '-methine-bis- (2-chloroaniline), 3,3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3,3' -dimethylbenzidine, 3,3 '-dimethoxybenzidine, 3,3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4,4 '-diaminodiphenyl sulfide, 4-chloroo-toluidine, 4,4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4,4 '-diaminodiphenylmethane, 4,4' -methylenebis (3-chloro-2, 6-diethylaniline), imazalil, thiabendazole, methylisothiazolinone, 1, 2-benzisothiazol-3-one, methylchloroisothiazolinone, cyproconazole, propiconazole, tebuconazole, imidacloprid, carbendazim, 2-octyl-4-isothiazolin-3-one, iodopropynyl butylcarbamate, melamine, benzoguanamine, caprolactam, isophoronediamine, 4,4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexanediamine, 11-aminoundecanoic acid, 4,4' -diaminodicyclohexylmethane, N, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, diethylhexyl adipate, cyclohexane 1, 2-diisononyl phthalate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, ultraviolet absorbent 320, ultraviolet absorbent 328, ultraviolet absorbent 3039, UV-9, benzophenone-12, benzophenone-6, 2- (dimethoxy) ethyl methacrylate, azacyclotridecane-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, 4,4' -dihydroxytetraphenylmethane, UV-24, UV-0, 4,4 '-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, parachlorometaxylenol, pentachlorophenol, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid, 4,4' -dihydroxytetraphenylmethane, 2, 4-dichloro-3, 5-dimethylphenol, 2,4, 6-trichlorophenol, parachlorometaxylenol, 4-chloro-3-cresol, terephthalic acid and 1, 4-cyclohexanedicarboxylic acid;
preparing a test solution: taking the contact material as a test sample, and carrying out pretreatment to obtain a test sample solution;
and (3) liquid chromatography-mass spectrometry detection: respectively detecting the standard working solution and the test solution by adopting a high performance liquid chromatography-quadrupole time-of-flight mass spectrometer;
and (4) judging a result: and comparing the detection result of the test solution with the detection result of the standard working solution to obtain a screening result of the risk substances.
2. The method of screening for a risk substance in a food contact material according to claim 1, wherein when the risk substance is selected from the group consisting of: 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, benzoguanamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane-1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, an antioxidant 1098, an antioxidant TH-1790, an ultraviolet absorbent 320, an ultraviolet absorbent 328, an ultraviolet absorbent 3039, UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate and 1, 4-butanediol glycidyl ether;
the following first chromatographic measurement conditions were selected:
a chromatographic column: hypersil GOLDTM，100mm×0.4mm，3μm；
Mobile phase 1: a: formic acid in 0.2 mL: 1L of water, B: as 0.156g ammonium acetate: 0.2mL of formic acid: 2mL of water: 200mL of isopropyl alcohol: preparing 800mL of methanol;
elution procedure 1: adjusting the flow rate and the proportion of the mobile phase B according to the following time points, wherein the flow rate and the proportion of the mobile phase B are changed in a linear gradient manner between the two time points;
Figure FDA0003525841930000021
when 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, di-n-butyl phthalate, di (2-methoxy) ethyl phthalate, di (2-butoxy) ethyl phthalate, di (2-cyclohexyl) phthalate, di (2-ethylhexyl) phthalate, di (2-n-octyl phthalate, diphenyl phthalate, dinonyl phthalate, diisononyl phthalate, 2, 6-diaminotoluene/2, 4-diaminotoluene, 2, 4-dimethylaniline, 2, 6-methylaniline, di-n-methylaniline, di-butyl phthalate, di (2-butyl) ethyl phthalate, di-benzyl phthalate, di (2-butyl) ethyl phthalate, di (2-butyl) ethyl phthalate, di-butyl-phthalate, di (2-butyl) ethyl phthalate, di-butyl-phthalate, di-butyl-phthalate, di-butyl-phthalate, di-butyl-ethyl phthalate, di-butyl-phthalate, di-butyl-phthalate, di-ethyl phthalate, di-butyl-phthalate, di-butyl-ethyl phthalate, di-butyl-phthalate, O-aminoazotoluene, p-aminoazobenzene, o-methoxyaniline, 4 '-methine-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-chloroo-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine, 4-aminobiphenyl, 4 '-diaminodiphenylmethane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazol-3-one, methylchloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, melamine, isophorone diamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexanediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azacyclotridecan-2-one;
the following second chromatographic measurement conditions were selected:
and (3) chromatographic column: hypersil GOLDTM，100mm×0.4mm，3μm；
Mobile phase 2: a: formic acid in 0.2 mL: 1L of water, B: formic acid in 0.2 mL: 1L of acetonitrile is prepared;
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, orthophenylphenol, 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, parachlorometaxylenol, pentachlorophenol, terephthalic acid 1, 4-cyclohexanedicarboxylic acid;
the following third chromatographic measurement conditions were selected:
a chromatographic column: hypersil GOLDTM，100mm×0.4mm，3μm；
Mobile phase 3: a: ammonia was added as 0.1 mL: 1L of water, B: ammonia was added as 0.1 mL: 1L of acetonitrile is prepared;
elution procedure 2: adjusting the flow rate and the proportion of the mobile phase B according to the following time points, wherein the flow rate and the proportion of the mobile phase B are changed in a linear gradient manner between the two time points;
Figure FDA0003525841930000031
3. the method for screening a hazardous substance in a food contact material according to claim 1, wherein in the LC-MS detection step, the following detection conditions are adopted: the CAD GAS was set at 4-7psi, both the GAS1 and GAS2 were set at 45-65psi, and the temperature was set at 500-.
4. The method of screening for risk substances in food contact materials and preparations according to claim 3, wherein when the risk substances are selected from the group consisting of: 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, benzoguanamine, caprolactam, diethylhexyl adipate, diisononyl cyclohexane-1, 2-dicarboxylate, tributyl acetylcitrate, trimethylolpropane trimethacrylate, antioxidant 1098, antioxidant TH-1790, ultraviolet absorbent 320, ultraviolet absorbent 328, ultraviolet absorbent 3039, UV-9, benzophenone-12, benzophenone-6, 2- (dimethylamino) ethyl methacrylate, 1, 4-butanediol glycidyl ether, 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 '-methine-bis- (2-chloroaniline), 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 2, 6' -diaminodiphenylmethane, 3,3' -dimethylbenzidine, 3' -dimethoxybenzidine, 3' -dichlorobenzidine, p-chloroaniline, 2,4, 5-trimethylaniline, 2-amino-4-nitrotoluene, o-toluidine, 2-naphthylamine, 4' -diaminodiphenyl sulfide, 4-chloroo-toluidine, 4' -diaminodiphenyl ether, benzidine, 3-amino-p-toluidine ether, 4-aminobiphenyl, 4' -diaminodiphenylmethane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), methylisothiazolinone, 1, 2-benzisothiazol-3-one, methylchloroisothiazolinone, 2-octyl-4-isothiazolin-3-one, m-ethylbenzisothiazolinone, p-toluidine, 4-aminotoluene, 4' -diaminodiphenylmethane, 4' -methylenebis (3-chloro-2, 6-diethylaniline), Melamine, isophoronediamine, 4 '-methylenebis (2-methylcyclohexylamine), 1, 6-hexanediamine, 11-aminoundecanoic acid, 4' -diaminodicyclohexylmethane, N-diethylethanolamine, triethanolamine, bis (2-hydroxypropyl) amine, triisopropanolamine, UV-9, azacyclotridecan-2-one;
the following mass spectrometric conditions were selected:
positive ion mode: and the 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 MSDefilling patent: 60V, TOF MSDP spread: 0V, TOF MS precision: 10V, TOF CE spread: 0V, TOF MSMS start mass: 50Da, TOF MSMS stop mass: 1000Da, TOF MSMS Accumulation Time: 0.1s, TOF MSMSMSMSMSMSMSSCLUSTERING Potential: 60V, TOF MSMSMSMSSDP spread: 0, TOF MSMS fusion 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, orthophenylphenol, 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, parachlorometaxylenol, pentachlorophenol, terephthalic acid, 1, 4-cyclohexanedicarboxylic acid;
the following mass spectrometric conditions were selected:
negative ion mode: the 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 MSDefilling patent: -60V, TOF MSDP spread: 0V, TOF MS condensation energy: -5V, TOF CE spread: 0V, TOF MSMS start mass: 50Da, TOF MSMS stop mass: 1000Da, TOF MSMS Accumulation Time: 0.1s, TOF MSMSMSMSSDecltiming patent: -60V, TOF msmssdp spread: 0, TOF MSMS fusion energy: 30V, TOF MSMS CE spread 15V.
5. The method for screening for a hazardous material in a food contact material according to claim 1, wherein in said mass spectrometric conditions, the detection is performed using the following detection ion pairs:
Figure FDA0003525841930000051
Figure FDA0003525841930000061
Figure FDA0003525841930000071
Figure FDA0003525841930000081
Figure FDA0003525841930000091
6. the method for screening a hazardous substance in a food contact material according to claim 1, wherein in the preparing of the standard solution, a standard stock solution is prepared with water, methanol or tetrahydrofuran as a solvent, and diluted with methanol, and a standard working solution is prepared in the following concentration ranges;
Figure FDA0003525841930000092
Figure FDA0003525841930000101
Figure FDA0003525841930000111
Figure FDA0003525841930000121
Figure FDA0003525841930000131
7. the method for screening dangerous substances in food contact materials according to claim 1, wherein in the step of preparing the test sample solution, the test sample is taken, the migration liquid of the food contact materials or the extract liquid of the test sample subjected to solvent extraction is obtained according to GB 5009.156 and GB 31604.1 standards, and the supernatant liquid is taken after the migration liquid or the extract liquid is centrifuged, so that the test sample solution is obtained.
8. The method of claim 1, wherein the LC-MS detection step is performed using an electrospray ion source and TOF MS or IDA scanning mode.
9. The method for screening a hazardous substance in a food contact material according to claim 1, wherein in the LC-MS detection step, the sample injection volume is 5 μ L in positive ion mode; the injection volume in the negative ion mode was 2. mu.L.
10. Use of the method of any one of claims 1-9 for screening for a substance at risk in food contact materials.
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