Study on determination of migratable nonvolatile substances from PET⁃containing food contact materials by using ultra⁃high performance liquid chromatography tandem quadrupole time⁃of⁃flight high⁃resolution mass spectrometry screening test

doi:10.19491/j.issn.1001-9278.2022.10.019

Abstract

Abstract:

Aiming to evaluate the potential migration risk substances in PET⁃contained food contact materials， an ultra⁃high performance liquid chromatography tandem quadrupole time⁃of⁃flight high⁃resolution mass spectrometry （UPLC⁃Q⁃TOF） was used to implement screening tests and analyze the unknown non⁃volatile substances migrated from four different types of PET⁃contained food contact materials in 4 % acetic acid and 50 % ethanol simulants. The main migration substances are oligomers formed by polymerized monomers and processing aids such as antioxidants and smooth agents， as well as the NIAS substances formed in the processing and migration processes. Pure materials such as pure PET have less migration substances， while multilayer composite materials have much more migration substances. In the food contact composite materials， the PET materials can be modified by adding adipic acid， sebacic acid， neopentyl glycol or other substances during production. In addition， some of the migrated substances may undergo alcoholysis or addition reaction with ethanol in the simulant， leading to the generation of new risk NIAS.

Key words: ultra?high performance liquid chromatography tandem quadrupole time?of?flight high?resolution mass spectrometry, food contact material, polyethylene gltcol terephthalate, migration, screening test

CLC Number:

TQ323.4

DENG Yuming, TANG Lei, LUO Shipeng. Study on determination of migratable nonvolatile substances from PET⁃containing food contact materials by using ultra⁃high performance liquid chromatography tandem quadrupole time⁃of⁃flight high⁃resolution mass spectrometry screening test[J]. China Plastics, 2022, 36(10): 131-137.

Figures/Tables 5

References 21

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时间/min	5 mmol/L甲酸铵含量/%	甲醇含量/%	流速/mL∙min^-1
0	98	2	0.3
8	0	100	0.3
17	0	100	0.3
17.1	98	2	0.3
20	98	2	0.3

时间/min	5 mmol/L甲酸铵含量/%	甲醇含量/%	流速/mL∙min^-1
0	98	2	0.3
8	0	100	0.3
17	0	100	0.3
17.1	98	2	0.3
20	98	2	0.3

样品编号	检出物质	分子式	CAS号	PET共混	塑⁃塑复合			铝⁃塑复合1		铝⁃塑复合2		毒性等级
样品编号	检出物质	分子式	CAS号	4 % HOAc	50 % EtOH	4 % HOAc	50 % EtOH	4 % HOAc	50 % EtOH	4 % HOAc	50 % EtOH	毒性等级
1^#	链［TPA+EG］	C₁₀H₁₀O₅	-	ND	Y	ND	ND	ND	Y	ND	Y	II
2^#	链［TPA+EG+TPA］	C₁₈H₁₄O₈	-	ND	Y	ND	ND	ND	Y	ND	Y	II
3^#	链［TPA+EG+TPA+EG］	C₂₀H₁₈O₉	-	ND	Y	ND	ND	ND	Y	ND	Y	II
4^#	链［TPA+EG+TPA+EG+TPA+EG］	C₃₀H₂₆O₁₃	-	ND	Y	ND	ND	ND	Y	ND	Y	II
5^#	链［TPA+Et］	C₁₀H₁₀O₄	-	ND	Y	ND	ND	ND	ND	ND	ND	II
6^#	链［TPA+EG+TPA+Et］	C₂₀H₁₈O₈	-	ND	Y	ND	ND	ND	ND	ND	ND	II
7^#	油酸	C₁₈H₃₄O₂	112⁃80⁃1	ND	ND	ND	Y	ND	ND	ND	ND	60 mg/kg
8^#	抗氧剂1076	C₃₅H₆₂O₃	2082⁃79⁃3	ND	ND	ND	Y	ND	ND	ND	ND	6 mg/kg
9^#	168氧化产物	C₄₂H₆₃O₄P	95906⁃11⁃9	ND	ND	ND	Y	ND	Y	ND	ND	III
10^#	十二酸二乙醇胺	C₁₄H₂₉NO₃	120⁃40⁃1	ND	ND	ND	Y	ND	ND	ND	ND	5 mg/kg
11^#	十四酸二乙醇胺	C₁₈H₃₇NO₃	7545⁃23⁃5	ND	ND	ND	Y	ND	ND	ND	ND	I
12^#	棕榈酸二乙醇胺	C₂₀H₄₁NO₃	7545⁃24⁃6	ND	ND	ND	Y	ND	ND	ND	ND	I
13^#	硬脂酸二乙醇胺	C₂₂H₄₅NO₃	93⁃82⁃3	ND	ND	ND	Y	ND	ND	ND	ND	I
14^#	亚油酸二乙醇胺	C₂₂H₄₁NO₃	56863⁃02⁃6	ND	ND	ND	Y	ND	ND	ND	ND	I
15^#	油酸二乙醇胺	C₂₂H₄₃NO₃	93⁃83⁃4	ND	ND	ND	Y	ND	ND	ND	ND	I
16^#	链［EG+HDA+EG］	C₁₀H₁₈O₆	-	ND	ND	ND	ND	ND	Y	ND	ND	II
17^#	环［EG+HDA+EG］	C₁₀H₁₆O₅	-	ND	ND	ND	ND	Y	Y	ND	ND	II
18^#	环［HDA+NPG］	C₁₁H₁₈O₄	-	ND	ND	ND	ND	Y	Y	ND	ND	II
19^#	环［HDA+EG+HDA+NPG］	C₁₉H₃₀O₈	-	ND	ND	ND	ND	Y	Y	ND	ND	II
20^#	环［HDA+EG+EG+HDA+NPG］	C₂₁H₃₄O₉	-	ND	ND	ND	ND	Y	Y	ND	ND	II
21^#	环［HDA+EG+EG+TPA+NPG］	C₂₃H₃₀O₉	-	ND	ND	ND	ND	ND	Y	ND	ND	II
22^#	环［HDA+EG+TPA+NPG］	C₂₁H₂₆O₈	-	ND	ND	ND	ND	ND	Y	ND	ND	II
23^#	环［HDA+NPG+ HDA+NPG］	C₂₂H₃₆O₈	-	ND	ND	ND	ND	Y	Y	ND	ND	II
24^#	环［TPA+NPG+ TPA+NPG］	C₂₆H₂₈O₈	-	ND	ND	ND	ND	ND	Y	ND	ND	II
25^#	环［HDA+NPG+ TPA+NPG］	C₂₄H₃₂O₈	-	ND	ND	ND	ND	ND	Y	ND	ND	II
26^#	环［TPA+EG+EG+ TPA+NPG］	C₂₅H₂₆O₉	-	ND	ND	ND	ND	ND	Y	ND	ND	II
27^#	二十碳酰胺	C₂₀H₄₁NO	51360⁃63⁃5	ND	ND	ND	ND	ND	Y	ND	ND	I
28^#	二十烯酰胺	C₂₀H₃₉NO	10436⁃08⁃5	ND	ND	ND	ND	ND	Y	ND	ND	I
29^#	二十二碳酰胺	C₂₂H₄₅NO	3061⁃75⁃4	ND	ND	ND	ND	ND	Y	ND	ND	I
30^#	芥酸酰胺	C₂₂H₄₃NO	112⁃84⁃5	ND	ND	ND	ND	ND	Y	ND	ND	60 mg/kg
31^#	芥酸	C₂₂H₄₂O₂	112⁃86⁃7	ND	ND	ND	ND	ND	Y	ND	ND	60 mg/kg
32^#	环［DDA+EG+DDA+NPG］	C₂₇H₄₆O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
33^#	环［DDA+NPG］	C₁₅H₂₆O₄	-	ND	ND	ND	ND	ND	ND	ND	Y	II
34^#	环［DDA+NPG+DDA+NPG］	C₃₀H₅₂O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
35^#	环［TPA+EG+DDA+NPG］	C₂₅H₃₄O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
36^#	环［TPA+NPG+DDA+NPG］	C₂₈H₄₀O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
37^#	环［TPA+NPG+TPA+NPG］	C₂₆H₂₈O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
38^#	甲苯⁃2，4⁃二氨基甲酸二乙酯	C₁₃H₁₈N₂O₄	-	ND	ND	ND	ND	ND	ND	ND	Y	III

样品编号	检出物质	分子式	CAS号	PET共混	塑⁃塑复合			铝⁃塑复合1		铝⁃塑复合2		毒性等级
样品编号	检出物质	分子式	CAS号	4 % HOAc	50 % EtOH	4 % HOAc	50 % EtOH	4 % HOAc	50 % EtOH	4 % HOAc	50 % EtOH	毒性等级
1^#	链［TPA+EG］	C₁₀H₁₀O₅	-	ND	Y	ND	ND	ND	Y	ND	Y	II
2^#	链［TPA+EG+TPA］	C₁₈H₁₄O₈	-	ND	Y	ND	ND	ND	Y	ND	Y	II
3^#	链［TPA+EG+TPA+EG］	C₂₀H₁₈O₉	-	ND	Y	ND	ND	ND	Y	ND	Y	II
4^#	链［TPA+EG+TPA+EG+TPA+EG］	C₃₀H₂₆O₁₃	-	ND	Y	ND	ND	ND	Y	ND	Y	II
5^#	链［TPA+Et］	C₁₀H₁₀O₄	-	ND	Y	ND	ND	ND	ND	ND	ND	II
6^#	链［TPA+EG+TPA+Et］	C₂₀H₁₈O₈	-	ND	Y	ND	ND	ND	ND	ND	ND	II
7^#	油酸	C₁₈H₃₄O₂	112⁃80⁃1	ND	ND	ND	Y	ND	ND	ND	ND	60 mg/kg
8^#	抗氧剂1076	C₃₅H₆₂O₃	2082⁃79⁃3	ND	ND	ND	Y	ND	ND	ND	ND	6 mg/kg
9^#	168氧化产物	C₄₂H₆₃O₄P	95906⁃11⁃9	ND	ND	ND	Y	ND	Y	ND	ND	III
10^#	十二酸二乙醇胺	C₁₄H₂₉NO₃	120⁃40⁃1	ND	ND	ND	Y	ND	ND	ND	ND	5 mg/kg
11^#	十四酸二乙醇胺	C₁₈H₃₇NO₃	7545⁃23⁃5	ND	ND	ND	Y	ND	ND	ND	ND	I
12^#	棕榈酸二乙醇胺	C₂₀H₄₁NO₃	7545⁃24⁃6	ND	ND	ND	Y	ND	ND	ND	ND	I
13^#	硬脂酸二乙醇胺	C₂₂H₄₅NO₃	93⁃82⁃3	ND	ND	ND	Y	ND	ND	ND	ND	I
14^#	亚油酸二乙醇胺	C₂₂H₄₁NO₃	56863⁃02⁃6	ND	ND	ND	Y	ND	ND	ND	ND	I
15^#	油酸二乙醇胺	C₂₂H₄₃NO₃	93⁃83⁃4	ND	ND	ND	Y	ND	ND	ND	ND	I
16^#	链［EG+HDA+EG］	C₁₀H₁₈O₆	-	ND	ND	ND	ND	ND	Y	ND	ND	II
17^#	环［EG+HDA+EG］	C₁₀H₁₆O₅	-	ND	ND	ND	ND	Y	Y	ND	ND	II
18^#	环［HDA+NPG］	C₁₁H₁₈O₄	-	ND	ND	ND	ND	Y	Y	ND	ND	II
19^#	环［HDA+EG+HDA+NPG］	C₁₉H₃₀O₈	-	ND	ND	ND	ND	Y	Y	ND	ND	II
20^#	环［HDA+EG+EG+HDA+NPG］	C₂₁H₃₄O₉	-	ND	ND	ND	ND	Y	Y	ND	ND	II
21^#	环［HDA+EG+EG+TPA+NPG］	C₂₃H₃₀O₉	-	ND	ND	ND	ND	ND	Y	ND	ND	II
22^#	环［HDA+EG+TPA+NPG］	C₂₁H₂₆O₈	-	ND	ND	ND	ND	ND	Y	ND	ND	II
23^#	环［HDA+NPG+ HDA+NPG］	C₂₂H₃₆O₈	-	ND	ND	ND	ND	Y	Y	ND	ND	II
24^#	环［TPA+NPG+ TPA+NPG］	C₂₆H₂₈O₈	-	ND	ND	ND	ND	ND	Y	ND	ND	II
25^#	环［HDA+NPG+ TPA+NPG］	C₂₄H₃₂O₈	-	ND	ND	ND	ND	ND	Y	ND	ND	II
26^#	环［TPA+EG+EG+ TPA+NPG］	C₂₅H₂₆O₉	-	ND	ND	ND	ND	ND	Y	ND	ND	II
27^#	二十碳酰胺	C₂₀H₄₁NO	51360⁃63⁃5	ND	ND	ND	ND	ND	Y	ND	ND	I
28^#	二十烯酰胺	C₂₀H₃₉NO	10436⁃08⁃5	ND	ND	ND	ND	ND	Y	ND	ND	I
29^#	二十二碳酰胺	C₂₂H₄₅NO	3061⁃75⁃4	ND	ND	ND	ND	ND	Y	ND	ND	I
30^#	芥酸酰胺	C₂₂H₄₃NO	112⁃84⁃5	ND	ND	ND	ND	ND	Y	ND	ND	60 mg/kg
31^#	芥酸	C₂₂H₄₂O₂	112⁃86⁃7	ND	ND	ND	ND	ND	Y	ND	ND	60 mg/kg
32^#	环［DDA+EG+DDA+NPG］	C₂₇H₄₆O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
33^#	环［DDA+NPG］	C₁₅H₂₆O₄	-	ND	ND	ND	ND	ND	ND	ND	Y	II
34^#	环［DDA+NPG+DDA+NPG］	C₃₀H₅₂O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
35^#	环［TPA+EG+DDA+NPG］	C₂₅H₃₄O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
36^#	环［TPA+NPG+DDA+NPG］	C₂₈H₄₀O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
37^#	环［TPA+NPG+TPA+NPG］	C₂₆H₂₈O₈	-	ND	ND	ND	ND	ND	ND	ND	Y	II
38^#	甲苯⁃2，4⁃二氨基甲酸二乙酯	C₁₃H₁₈N₂O₄	-	ND	ND	ND	ND	ND	ND	ND	Y	III

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