3种聚烯烃抗氧剂迁移的试验分析及数值模拟

聚烯烃是食品包装广泛应用的一类塑材,抗氧剂又是聚烯烃塑材最常使用的一类添加剂,因此抗氧剂向食品的迁移是影响食品安全的重要因素.借助HPLC分析仪器试验研究了不同温度条件下3种抗氧剂BHT、Irganox 1076及Irgafos 168向100%乙醇的迁移,并对实验值与数值模拟结果作了对比分析.     

聚烯烃抗氧剂1076和168在食用油中的迁移研究

借助HPLC分析仪器试验研究了不同温度下聚烯烃抗氧剂1076和168向食用调和油、玉米油和菜籽油的迁移,讨论了不同油类、温度对迁移的影响,并将所得结果与用100%乙醇作为脂肪模拟物取得的结果进行对比.结果表明:油的种类对抗氧剂的迁移过程影响较小;温度对迁移动力学过程起到决定性作用,迁移速度随温度的升高而加快,达到迁移平衡所需的时间也越短;2种抗氧剂在食用油和100%乙醇中的迁移行为相似,总体说来100%乙醇可以作为脂肪模拟物来替代食用油用于抗氧剂的迁移试验研究.     

食品接触用纸制品中3-氯-1,2-丙二醇特定迁移量的测定

本文建立了食品接触用纸制品中3-氯-1,2-丙二醇在4%乙酸、10%乙醇和异辛烷3种食品模拟物中特定迁移的测定方法。采用食品模拟物浸泡,正己烷萃取,再经七氟丁酰基咪唑衍生,用气相色谱质谱法分析。在所选择的试验条件下,方法的线性良好,检出限低,测试样品的精密度和回收率也符合要求。     

PE淋膜纸中UV墨光引发剂向食品模拟物的迁移行为

研究聚乙烯(PE)淋膜纸4015、4025纸中紫外光(UV)固化墨光引发剂1-羟基环己基苯基甲酮(184)和2,2-二甲氧基-苯基甲酮(651)通过PE淋膜层向不同温度20℃、40℃和60℃、不同食品模拟物10%乙醇、95%乙醇和异辛烷中的迁移行为。探讨温度、迁移物分子结构、食品模拟物的溶胀、PE淋膜量对纸塑复合包装材料纸中具有不同分子结构的污染物通过不同厚度聚合物涂层向食品模拟物迁移的影响,从微观角度解释其影响因素。     

微波条件下聚烯烃抗氧剂向脂肪食品模拟物的迁移研究

微波加热时,食品能快速达到高温并将热量传递给外部包装,从而加速包装材料内化学物向食品的迁移.借助微波光纤测微系统MWS(加拿大,FISO Technologies)试验研究了不同微波功率条件下抗氧剂BHT、Irganox 1076及Irgafos 168向6种食用油(大豆油、花生油、葵花籽油、玉米油、菜籽油和食用调和油)的迁移.     

可降解包装材料中ATBC的迁移规律

目的 研究基于PLA/PBAT可生物降解食品保鲜袋中成分的测定,以及其中增塑剂乙酰柠檬酸三丁酯(ATBC)的迁移规律.方法 采用气相色谱-质谱联用仪检测材料中的成分及向食品模拟物中的迁移情况,并以此为基础,研究不同温度、不同厚度、不同时间、不同模拟物对ATBC迁移规律的影响;并采用红外光谱和扫描电镜从微观分析薄膜浸泡前后的变化.结果 在温度和厚度相同的条件下,ATBC在体积分数为95％的乙醇中迁移量最大;在同一种食品模拟物中,温度越高、时间越长,ATBC的迁移量越大;在温度和食品模拟物保持相同的条件下,厚度越小,ATBC的迁移量越大.结论 食品模拟物的性质、温度、厚度和时间都是影响ATBC迁移行为的重要因素.     

影响PE淋膜纸中化学迁移物分配系数的因素

利用迁移平衡实验,通过研究不同温度(40℃和60℃)条件下、不同纸塑复合包装材料4015、6515和3312纸中不同的化学物紫外光(UV)固化墨光引发剂1-羟基环己基苯基甲酮(184)和2,2-二甲氧基-苯基甲酮(651),向不同的食品模拟物10%乙醇、95%乙醇和异辛烷的迁移,分析讨论温度、食品模拟物、化学物分子结构和纸张性质对纸塑界面处化学物分配系数的影响。结果发现,温度升高,分配系数减小;化学物分子结构越复杂,分配系数越大;松厚度大、紧度小、孔隙率高的纸张,分配系数小;食品模拟物本身的极性、对包装材料的溶胀性及对化学物的溶解性等对分配系数影响很大。     

邻苯二甲酸酯增塑剂在可得然包装膜中的迁移研究

以可得然包装膜代表生物基包装材料,选取邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二正丁酯(DBP)以及邻苯二甲酸二(2-乙基己)酯(DEHP)为研究对象,使用气相色谱-质谱联用(GC-MS)法测定增塑剂的迁移量,研究了增塑剂质量分数分别为0.1％、0.5％、1％和3％的可得然薄膜,在低温(4℃)、常温(25℃)与高温(40℃)条件下向正己烷、50％乙醇、4％乙酸和蒸馏水食品模拟物中的迁移规律,并利用Weibull分布函数分别建立3种增塑剂在正己烷中的迁移模型.结果发现,3种增塑剂在4种食品模拟物中的迁移量由大到小依次为:正己烷、50％乙醇、4％乙酸、蒸馏水.随着时间的延长,增塑剂的迁移量先逐渐增加,在第3 d达到迁移平衡,迁移量达到最大值.随着温度的升高,增塑剂的迁移量不断增加,初始添加量越大,其迁移量越大.3种增塑剂在正己烷中更易发生迁移,在实际应用中应避免接触油性食品.建立了DMP、DBP和DEHP基于Cm、τ和β三参数的Weibull迁移模型,具有一定的预测性,可用来快速预测邻苯二甲酸酯类增塑剂的迁移量.     

食品用塑料包装中双酚F和双酚S迁移规律的分析

研究食品用塑料包装中双酚F和双酚S的迁移规律。通过液相色谱串联质谱法测定相同样品在不同模拟物中(10%乙醇、4%乙酸、50%乙醇和橄榄油)双酚F和双酚S的迁移量,分析模拟物、迁移温度、迁移时间、接触面积与模拟物体积比和迁移次数对双酚F和双酚S迁移量的影响。结果表明:迁移条件一致时,双酚F和双酚S在4种模拟物中的迁移量大小为50%乙醇10%乙醇4%乙酸橄榄油;模拟物一致时,双酚F和双酚S的迁移量随迁移温度的升高、迁移时间的延长、接触面积与模拟物体积比的增大而增加,随迁移次数的增加而减少。反映模拟物的属性、温度、时间、接触面积与模拟物体积比和迁移次数均影响双酚F和双酚S的迁移量。     

用气相色谱分析PET瓶中化合物的迁移

用二氯甲烷作为溶剂,以大数量级把氯苯和苯酚浸泡入洁净PET薄片中.而后,分别用4种食品模拟液(正己烷、15%乙醇、3%醋酸和蒸馏水)浸泡制备好的PET薄片.用气相色谱分析测定不同时间下4种食品模拟液中氯苯和苯酚的迁移量,为迁移模型分析提供一定的实验数据.     

Degradation of Irgafos 168 and migration of its degradation products from PP‐R composite films

Food contact materials contain non‐intentionally added substances from degradation, and reaction processes could rise food safety problems. Three polypropylene random copolymer composite films were prepared by extruding the polypropylene random copolymer matrix with Irgafos 168, Irgafos 168 and nanocopper, Irgafos 168 and KH550 modified nanocooper, respectively. To evaluate the degradation behaviors of Irgafos 168, the films were treated by UV irradiation, microwave treatment, sunlight exposure, placed in different oxygen concentration conditions, suffered the extrusion process, and high temperature. Migration test was conducted at 20°C, 40°C, and 70°C with films tested in food simulant. GC‐MS was adopted to determine the concentration of Irgafos 168 and its two degradation products, 2,4‐di‐tert‐butylphenol (DP1) and tris (2,4‐di‐tert‐butylphenyl) phosphate (DP2). UV irradiation significantly accelerated the degradation of Irgafos 168 compared with other treatments; DP1 and DP2 increased to maximum value at 24 hours and decreased afterwards, simultaneously. The introduction of nanocopper notably promoted DP1 generation after extrusion whereas suppressed DP2 generation which also caused a higher degradation rate of Irgafos 168 and sharp decrease of DP1 under microwave treatment, sunlight exposure, and high temperature treatment. No significant difference between the effects of nanocopper and KH550 modified nanocopper on degradation of Irgafos 168 was found. For the migration test, the introduction of nanocopper inhibited the migration of Irgafos 168 and DP2 whereas promoted the migration of DP1. No significant difference between the introduction of nanocopper and KH550 modified nanocopper on migration of Irgafos 168 and DP1, DP2 was found.     

Investigations on Overall Migration of Various Plastic Materials and Articles Used in Contact with Foodstuffs

The results of overall migration tests for a wide range of plastic packagings and other domestic and imported articles made of plastic intended to come into direct contact with foodstuffs are presented. In these tests the simulants specified in Directive 85/572/EEC as well as isooctane and 95% ethanol (so called alternative substances) have been used. Checking the overall migration into the four simulants specified in the above mentioned Directive it was found that the limit (equal to 10 mg/dm² according to Directive 90/128/EEC) was exceeded in a few, very specific, cases. Comparison between overall migration from some articles into sunflower oil and isooctane was also examined. The results indicate that though the use of isooctane as an alternative substance significantly simplifies the testing procedure, exceeding an overall migration limit into isooctane is not equivalent to exceeding the limit of migration into sunflower oil. In such cases only migration into typical fatty food simulants can have a deciding meaning. © 1997 John Wiley & Sons, Ltd.     

Changes of thermal properties and microstructure of nano‐ZnO/polylactic acid composite films during Zn migration

In this study, polylactic acid (PLA) films with different nano‐ZnO concentration (0, 1, 3, 5, 7, 9, and 15%wt) were obtained by casting method. Overall migration values and specific migration values were studied in different food simulants (10% [v/v] ethanol and isooctane). The results demonstrated that overall migration of the composite films and specific migration of Zn²⁺ was higher in 10% (v/v) ethanol solution than in isooctane solution. The release of Zn²⁺ was affected by the percentage of nano‐ZnO in the composite films and food simulants. The migration of Zn in this study was mainly caused by polymer softening and degradation leading to the dissolution of Zn. Scanning electron microscope analysis indicated that with the migration of Zn²⁺, the structure of the composite films changed greatly. Differential scanning calorimeter analysis indicated that the thermal stability was decreased and the glass transition temperature and crystallization temperature were reduced.     

食品包装材料HDPE中4种紫外吸收剂的迁移规律研究

在不同的条件下,将含有已知量紫外吸收剂的HDPE膜,在水、10%(体积分数)乙醇溶液,3 g/L乙酸水溶液和精炼橄榄油等4种食品模拟物中浸泡,于一定的时间点吸取少量浸泡液,采用超高效液相色谱法测定紫外吸收剂的含量,研究迁移行为与浸泡时间、温度、食品模拟物属性、紫外吸收剂初始浓度、材料厚度等参数的关系。结果表明:紫外吸收剂只在脂肪类食品模拟物迁出;迁移率和迁移量随温度升高而增加;材料厚度增加,迁移量增大,迁移率降低;紫外吸收剂初始浓度越高,则迁移量越大,迁移率越低。     

Migration of Cyclic Monomer and Oligomers from Polyamide 6 and 66 Food Contact Materials into Food and Food Simulants: Direct Food Contact

Cyclic monomer and oligomers are the major migrating substances from polyamide (PA) food contact materials. An increase of caprolactam (+44%) and cyclic oligomer content (+27%, incl. caprolactam) in PA6 was observed by thermal treatment, here by extrusion of a PA6 film from a granulate. Migration experiments with a PA6 and a PA66 packaging film were carried out into food simulants according to directives 85/572/EEC and 82/711/EEC. Contact conditions (2 h/100°C) were chosen for a heat treatment of the food in the packaging, in this case production of scalded sausage. Aqueous and ethanolic food simulants clearly revealed to be the worst case for migration of cyclic PA6 and PA66 monomer and oligomers. Migration of cyclic oligomers into oil was one order of magnitude lower. No migration could be observed into isooctane (<8 µg dm^?2). The substitutes for oil, 95% ethanol and isooctane, were inapplicable for simulating migration of cyclic oligomers into oil. Caprolactam showed different migration behaviour compared with cyclic oligomers, migrating into oil and water to the same extent depending on contact conditions. Fifty percent of the extractable caprolactam migrated from a PA6 sausage casing into scalded sausage (4.2 mg kg^?1), residual 41% apparently were extracted by the boiling medium or during pretreatment (soaking) of the casing. Potential migration of caprolactam and cyclic oligomers from a PA6 tea bag was found to be 18% of the specific migration limit for caprolactam and 36% of the overall migration limit. Copyright © 2014 John Wiley & Sons, Ltd.     

食品接触材料中多种添加剂迁移量的测定

目的建立食品接触材料中32种添加剂迁移量的高效液相色谱检测方法,调查市售塑料食品接触材料中32种添加剂的迁移水平。方法选取103批不同材质的塑料食品接触材料,采用异辛烷、乙醇(体积分数分别为50%,20%,10%)、质量分数为3%的乙酸浸泡样品,得到模拟液,用液相色谱仪分析,外标法定量。结果 DBP,DEHP,二苯酮,UV-1577,BHT,697,2246,BHEB和荧光增白剂184均有检出,其中11批PVC样品中DBP或DEHP、1批PP样品中二苯酮和1批PC样品中UV-1577的迁移量高于限量要求。上述添加剂在异辛烷模拟物中的检出率最高,在体积分数为50%的乙醇模拟物中有较低的检出率,在其他3种模拟物中均未检出。结论塑料食品接触材料不宜直接用于接触油类食品和浓度较高的酒类食品。PP材质中的二苯酮、PC材质中的UV-1577、PVC材质中的DBP和DEHP存在的潜在危害较大,应加强监管。     

A systematic study on the stability of UV ink photoinitiators in food simulants using GC

Several studies have been published on the stability of plastic monomers and additives in food simulants. However, there are practically no published results about the stability of ink components in food simulants. In this work, the stability of two ultraviolet (UV) ink photoinitiators (PIs) in one aqueous and in two substitute fat food simulants was studied under various time–temperature conditions. Furthermore, the addition of the stabilizing agent hydroquinone monomethyl ester (HQMME) in the same conditions was considered as a comparative experiment. The PIs tested were 1‐hydroxycyclohexyl‐1‐phenyl ketone (Irgacure‐184) and benzyldimethyl ketal (Irgacure‐651). The various test conditions included exposure of 10 days to temperatures of 20, 40 and 60°C for 10% ethanol and 95% ethanol simulants, and exposure of 2 days to temperatures of 20, 40 and 60°C for isooctane. Following exposure to these conditions, the additive samples were analysed. The extracts of samples exposed to various temperature conditions as well as unexposed spiked controls and blanks were analysed by gas chromatography (GC) on a non‐polar (5%‐phenyl)‐methylpolysiloxane capillary column. The results showed that the protective effect of HQMME was not obvious in all test conditions under dark conditions. The Irgacure‐184 was quite stable under all test conditions whether the stabilizing agent was added or not. Irgacure‐651 was stable almost under all test conditions, except in 10% ethanol at 60°C. The mass spectrum of decomposed product of Irgacure‐651 was detected by GC‐MS (Mass Spectrum), and the structure of the decomposed product was obtained by mass spectrographic analysis. The method of detection and disposal is also applicable for UV ink PI migration testing from several different paper or paperboard‐plastic coating layer materials into the food simulants used in the study. Copyright © 2008 John Wiley & Sons, Ltd. 2008     

Research note — migration of antioxidants from polyolefins into ethanolic simulants

Polyolefins such as low density polyethylene are widely used as food packaging materials. Antioxidant additives are added to such polymers to prevent oxidative reactions during thermal processing. The migratory behaviour of Irganox 1076 and Irgafos 168 from LLDPE into several ethanolic simulating agents, in which the ethanol content ranged from 40–100%, and at different temperatures was investigated. Higher migration values were found at higher ethanol contents with a strong increase between 50 and 75% ethanol. An Arrhenius type relationship was found for these antioxidants with faster migration at higher temperatures. © 1998 John Wiley & Sons, Ltd.