目的 通过自行制备阳性样品的方式,研究聚氯乙烯塑料（PVC）塑料中乙酰柠檬酸三丁酯的（ATBC）添加量、残留量和迁移量三者间的关系,为有效控制PVC中ATBC的安全风险提供技术支持。方法 为准确测试PVC垫片中ATBC的残留量,首先建立溶解-沉淀-气相色谱-质谱检测方法,样品经四氢呋喃溶解后,加入乙腈沉淀溶液中的大分子化合物,再将清液用GC-MS法测定,得到PVC中ATBC的残留量,并对ATBC残留量方法进行方法学验证。PVC中ATBC迁移量的测定采用已有文献的方法。对自行制备的分别添加了2%、5%、10%、20%、30%、40%、50%ATBC的PVC塑料垫片分别进行残留量和迁移量测试,研究添加量、残留量和迁移量三者之间的关系。结果 新建立的ATBC残留量检测方法在0.20~5.0 mg/L范围内线性关系良好,相关系数达0.998,方法检出限为5 mg/kg,定量限为20.0 mg/kg,加标回收率为95.6%~102%,相对标准偏差（n=6）为3.7%~6.8%。对自行加工的阳性样品进行残留量和迁移量测试,发现ATBC残留量和迁移量均与添加量呈显著的正相关性。当添加量处于相同水平时,ATBC在4%乙酸和20%乙醇中的迁移水平较低,而在橄榄油和异辛烷中的迁移水平较高。当ATBC的添加量达到30%时,其在橄榄油和异辛烷中的迁移风险已接近超标水平,需引起关注;当添加量达到50%时,在橄榄油和异辛烷中的迁移量超过限量要求。结论 本研究将为瓶盖用PVC垫片的生产企业科学控制ATBC添加量,做好ATBC迁移量的合规管控提供科学的数据支持。
Abstract
The work aims to study the relationship between the addition amount, residual amount, and migration amount of acetyl tributyl citrate (ATBC) in polyvinyl chloride (PVC) plastics by preparing positive samples so as to provide technical support for production enterprises to effectively control the safety risks of ATBC in PVC. To accurately test the residual amount of ATBC in PVC gaskets, a dissolution precipitation gas chromatography-mass spectrometry detection method was first established. After dissolving the sample in tetrahydrofuran, the large molecular compounds in the acetonitrile precipitation solution were added, and the clear solution was determined by GC-MS to obtain the residual amount of ATBC in PVC. Using literature review methods, the migration amount of ATBC in different food simulants in the sample was determined. Residual and migration tests were conducted on PVC plastic gaskets prepared by ourselves with 2%, 5%, 10%, 20%, 30%, 40%, and 50% ATBC added. The methodological validation of the newly established ATBC residue determination method showed a good linear relationship and correlation coefficient within the range of 0.20-5.0 mg/L, the correlation coefficient reached 0.998. The residue method detection limit was 5.0 mg/kg and quantification limit was 20 mg/kg, the spiked recovery rate was 95.6%-102%, and the relative standard deviation (n=6) was 3.7%-6.8%. The residue and migration test of positive samples processed by themselves showed that the residue and migration of ATBC were significantly positively correlated with the addition amount. When addition amount was at the same level, the migration level of ATBC in 4% acetic acid and 20% ethanol was low, while the migration level in olive and isooctane was high. When the addition amount of ATBC reached 30%, its migration risk in olive oil and isooctane approached the overstandard level, which needed to be concerned. When the addition amount reached 50%, the migration amount in olive oil and isooctane exceeded the limit requirement. This research will provide scientific data support for the scientific control of the addition amount of ATBC and the compliance control of the migration amount of ATBC in the production enterprises of PVC gaskets for caps.
关键词
聚氯乙烯（PVC） /
乙酰柠檬酸三丁酯（ATBC） /
添加量 /
残留量 /
迁移量
Key words
polyvinyl chloride (PVC) /
acetyl tributyl citrate (ATBC) /
addition amount /
residue amount /
migration
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参考文献
[1] 蒋平平, 崇明本, 张典鹏, 等. 加快我国新型环境友好增塑剂柠檬酸酯研究与应用[J]. 塑料助剂, 2003(5): 1-8.
JIANG P P, CHONG M B, ZHANG D P, et al.Accelerate the Research and Application of a New Environmentally Friendly Plasticizer Citrate in China[J]. Plastic Additives, 2003(5): 1-8.
[2] 张丽. 柠檬酸酯类增塑剂的市场现状及前景[J]. 塑料助剂, 2008(1): 10-11.
ZHANG L.The Present Situation and Prospect of Citrate Plasticizers[J]. Plastics Additives, 2008(1): 10-11.
[3] 康永. 环保型增塑剂乙酰柠檬酸三丁酯的性能及发展前景[J]. 上海塑料, 2016, 44(1): 12-15.
KANG Y.Performance and Development Prospects of Acetyl Tributyl Citrate Ester as Environment Friendly Plasticizer[J]. Shanghai Plastics, 2016, 44(1): 12-15.
[4] 杨学军, 胡晓青, 王亭亭, 等. 基于PLA淋膜纸杯新风险项目的分析研究[J]. 造纸科学与技术, 2025, 44(2): 23-26.
YANG X J, HU X Q, WANG T T, et al.Analysis and Research on the New Risk Factors of PLA-Coated Paper Cup[J]. Paper Science & Technology, 2025, 44(2): 23-26.
[5] 尹静波, 鲁晓春, 曹燕琳, 等. 柠檬酸酯增塑改性聚乳酸[J]. 高分子材料科学与工程, 2008, 24(1): 151-154.
YIN J B, LU X C, CAO Y L, et al.Preparation and Characterization of Plasticized Poly(lactic acid): Citrate Esters as Plasticizers[J]. Polymer Materials Science & Engineering, 2008, 24(1): 151-154.
[6] 王悦, 金祥飞, 周新宇, 等. PVC输液器中环己酮和增塑剂ATBC的迁移性质研究[J]. 塑料工业, 2016, 44(7): 84-87.
WANG Y, JIN X F, ZHOU X Y, et al.Study on the Migration of Cyclohexanone and Plasticizer ATBC in PVC Infusion Set[J]. China Plastics Industry, 2016, 44(7): 84-87.
[7] 张智力, 高勇, 唐孔科, 等. 气相色谱法测定PVDC薄膜中的癸二酸二正丁酯和乙酰柠檬酸三丁酯[J]. 塑料科技, 2019, 47(7): 107-110.
ZHANG Z L, GAO Y, TANG K K, et al.Determination of DBS and TBAC in PVDC Film by Gas Chromatography[J]. Plastics Science and Technology, 2019, 47(7): 107-110.
[8] 国家卫生和计划生育委员会. 食品安全国家标准食品接触材料及制品用添加剂使用标准: GB 9685— 2016[S]. 北京: 中国标准出版社, 2017: 10.
National Health Commission of the People's Republic of China. National Food Safety Standard, Standards for the Use of Additives in Food Contact Materials and Products: GB 9685-2016[S]. Beijing: Standards Press of China, 2017: 10.
[9] 刘旭东, 朱思洁, 刘良禹, 等. 乙酰柠檬酸三丁酯围产期暴露对子代小鼠认知能力的影响[J]. 生态毒理学报, 2021, 16(5): 249-258.
LIU X D, ZHU S J, LIU L Y, et al.Effects of Perinatal Exposure of Acetyl Tributyl Bitrate on Cognitive Ability of Offspring Mice[J]. Asian Journal of Ecotoxicology, 2021, 16(5): 249-258.
[10] 刘旭东, 张智淮, 杨建邦, 等. 增塑剂乙酰柠檬酸三丁酯暴露对学习记忆能力的影响及VE保护作用[J]. 食品工业科技, 2021, 42(12): 233-239.
LIU X D, ZHANG Z H, YANG J B, et al.Effects of Plasticizer Acetyl Tributyl Citrate Exposure on Learning and Memory Abilities and Protective Effects of Vitmain E[J]. Science and Technology of Food Industry, 2021, 42(12): 233-239.
[11] 刘佳玺. 食品包装材料中柠檬酸酯类塑化剂对细胞毒性效应的研究[D]. 西安: 西安理工大学, 2021.
LIU J X.Study on The Toxic Effects of Citrate Plasticizers In Food Packaging Materials on Cells[D]. Xi'an: Xi'an University of Technology, 2021.
[12] 国家卫生健康委员会, 国家市场监督管理总局. 食品安全国家标准食品接触材料及制品迁移试验通则: GB 31604.1—2023[S]. 北京: 中国标准出版社, 2023: 9.
National Health Commission of the People's Republic of China, State Administration for Market Regulation. National Food Safety Standard General Principles for Migration Testing of Food Contact Materials and Products: GB 31604.1-2023[S]. Beijing: Standards Press of China, 2023: 9.
[13] EN1186-1:2002[s].N1186-1:2002[s]. European Committee for Standardization, 2002: 4.
[14] 国家卫生和计划生育委员会. 食品安全国家标准食品接触材料及制品迁移试验预处理方法通则: GB 5009.156—2016[S]. 北京: 中国标准出版社, 2017: 10.
National Health Commission of the People's Republic of China. National Food Safety Standards General Rules for Pretreatment Methods for Migration Tests of Food Contact Materials and Products: GB 5009.156-2016[S]. Beijing: Standards Press of China, 2017: 10.
[15] 刘仕途, 曾铭, 陈湘颖, 等. 气相色谱-质谱法测定食品接触材料及制品中4种柠檬酸酯类化合物的迁移量[J]. 分析试验室, 2024, 43(4): 463-468.
LIU S T, ZENG M, CHEN X Y, et al.Determination of Migration of Four Citrate Compounds in Food Contact Materials and Products by Gas Chromatography-Mass Spectrometry Method[J]. Chinese Journal of Analysis Laboratory, 2024, 43(4): 463-468.
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