塑料食品包装材料中常用抗氧化剂迁移研究进展

简介几种常用食品塑料包装材料及其常用抗氧化剂,重点介绍国内外学者对于食品接触塑料包装材料中4种常用抗氧化剂(BHT、Irganox1010、Irganox1076、Irgafos168)向食品(模拟物)的迁移研究现状及结论。同时对目前抗氧化剂迁移研究存在的问题和未来的发展趋势进行展望。     

纳米银-聚乙烯复合包装中银对2 种抗氧化剂向食品模拟物迁移的影响

探究纳米银-聚乙烯复合包装中纳米银成分的存在对2 种抗氧化剂（Irganox1076和Irgafos168）向食品模拟物迁移规律的影响。将含有抗氧化剂的聚乙烯包装膜和同时含有抗氧化剂与纳米银的复合包装膜裁成正方形若干,分别浸泡于正己烷和体积分数95%乙醇溶液2 种食品模拟物中,密封后在20、40 ℃以及70 ℃条件下进行迁移实验。食品模拟物中2 种抗氧化剂的加标回收率在79.3%～108.0%之间,相对标准偏差在0.7%～5.3%之间。2 种抗氧化剂的迁移会随着迁移温度的升高以及迁移时间的延长而增加直至达到迁移平衡,且其在正己烷模拟物中的迁移量大于在体积分数95%乙醇模拟物中的迁移量;含纳米银聚乙烯塑料比不含纳米银聚乙烯塑料中的抗氧化剂向食品模拟物中的迁移量小,表明纳米银成分的存在可以抑制包装中的抗氧化剂向食品模拟物中的迁移。     

微波条件下聚烯烃抗氧剂向食用油迁移的扩散系数研究

实验研究不同微波加热功率条件下PE膜内三种不同分子量不同分子结构的抗氧化剂(BHT、Irganox 1076和Irgafos 168)向6 种食用油的迁移,计算相应的扩散系数并给出其与微波加热功率的关系图。鉴于微波加热条件下迁移的特殊性,提出构建新的扩散系数预测模型的设想。     

模拟液的极性对聚丙烯中抗氧化剂迁移的影响

研究了4种抗氧化剂BHA、BHT、Irganox1076、Irgafos168从聚丙烯塑料迁移至6种不同极性的模拟液时,模拟液极性对抗氧化剂迁移规律的影响。结果表明,抗氧化剂与聚丙烯塑料相溶性越差,与模拟液相溶性越好,迁移平衡分配系数越大;同时,模拟液极性越接近聚丙烯时,迁移扩散系数越高,扩散系数受分子量影响越小,反之,则迁移扩散系数受分子量影响较大,扩散系数随分子量的增大而减小;无水乙醇模拟液中,抗氧化剂分子量越大,平衡分配系数受温度影响越大,迁移焓变随分子量增大而增大,而正己烷模拟液中变化正好与之相反。     

石墨烯/聚乙烯复合食品包装膜中两种紫外吸收剂向食品模拟物的迁移研究

目的:探究了石墨烯/低密度聚乙烯复合包装材料中两种紫外吸收剂UV-531和UV-P向脂肪类食品模拟物(异辛烷)的迁移规律。方法:利用气相色谱-质谱联用(GC-MS)建立了石墨烯/低密度聚乙烯复合食品包装薄膜中两种紫外线吸收剂UV-531和UV-P的检测方法,确定了甲苯溶解提取的方法。结果:在一定范围内,随着时间、温度和紫外线吸收剂质量浓度的增加,两种紫外线吸收剂向异辛烷的迁移量不断增加;石墨烯的加入阻碍了两种紫外线吸收剂向异辛烷的迁移;此外,两种紫外线吸收剂相互作用较小,对彼此向异辛烷的迁移基本没有影响。结论:石墨烯的加入可有效阻止两种紫外吸收剂向食品模拟物中的迁移。     

热力学数学模型对塑料中化学物向食品模拟液中迁移平衡时分配系数的预测研究

目的分配系数能够直接反映出塑料包装材料中有害化学物向食品迁移的水平,研究分配系数与塑料包装材料、迁移物及食品(模拟物)三者之间的关系有重要意义。方法以Scatchard-Hildebrand统计热力学理论为基础,从热力学平衡角度分析了化学物在包装材料/食品体系中的迁移和分配过程,建立了一个预测化学物迁移平衡时分配系数的热力学数学模型。通过所建立的初级数学模型对聚乙烯薄膜中四种抗氧化剂,即2,6-二叔丁基-4-甲基苯酚(BHT)、二丁基羟基茴香醚(BHA)、Irganox1010和Irganox1076向脂肪类食品模拟物异辛烷迁移平衡时状态进行模拟计算,并与已公开发表的实验数据进行了对比。结果聚乙烯薄膜中四种抗氧剂向异辛烷中迁移平衡的分配系数模拟值与实验值随温度变化趋势一致。结论该热力学模型符合迁移理论,对PE/抗氧剂/脂肪类食品体系分配系数的预测有一定的适用性。     

HDPE膜中抗氧剂1076向替代脂肪类食品模拟物迁移的研究

比较了HDPE膜中的抗氧剂1076分别向异辛烷与95%乙醇迁移的规律.结果表明:1076的迁移具有时间性,并受温度的影响.迁移物在食品包装材料与食品/食品模拟物之间的分配,不仅取决于三者的极性,还与温度和模拟物的分子量大小有关.含有1076的HDPE薄膜在实际使用过程中,应当避免包裹高脂肪类食品,以免引起抗氧剂高迁移问题.     

食品药品包装材料中抗氧化剂毒理学研究

对食品药品包装材料中常用抗氧化剂2,6-二叔丁基对甲苯酚(BHT)、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(Irganox 1010)、β-(3,5-二叔-4-羟基苯基)丙酸正十八碳醇酯(Irganox 1076)、三(2,4-二叔丁基苯基)亚磷酸酯(Irgafos 168)安全性进行毒理学评价.采用急性毒性试验、小鼠骨髓微核试验、小鼠精子畸形试验和30 d喂养试验进行毒性评价.结果表明:小鼠经口LD50等于11 340 mg/kg·BW;小鼠骨髓微核试验、小鼠精子畸形试验结果为阴性;30 d喂养试验未见大鼠的生长发育、血液学、生化、脏器比及组织病理学有异常变化.4种抗氧化剂混合物急性毒性分级属无毒级,无染色体损伤作用,无精子损害作用,无显著亚慢性毒性.     

超高效液相色谱测定市售塑料食品包装中的抗氧化剂

本实验对塑料包装中的叔丁基对羟基茴香醚（BHA）、2,6-二叔丁基对甲酚（BHT）、 β-（4．羟基-3,5．二叔丁基苯基）丙酸正十八酯（irganox 1076）三种酚类抗氧化剂进行了研究。快速溶剂萃取（ASE）方法提取市售塑料食品包装中的抗氧化剂后,利用超高效液相色谱（UPLC）对其含量进行测定。结果显示大部分市售食品塑料包装中含有BHT及Irganox1076,基本不含BHA。     

食品包装材料中邻苯二甲酸酯的迁移规律研究

目的研究不同食品包装材料中邻苯二甲酸酯(phthalate esters,PAEs)的迁移规律。方法采用气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)对不同温度、不同时间条件下PAEs从食品包装材料中向水、4%乙酸、50%乙醇与异辛烷食品模拟物中的迁移规律进行研究。结果 PAEs的迁移受食品模拟溶液、温度、时间、包装材料的影响。不同食品模拟物中迁移率为:异辛烷50%乙醇4%乙酸≈水;在同一种食品模拟物中,随着迁移时间延长和温度增加PAEs迁移量增大,温度越高迁移速率越快;食品包装材料的材质不同,PAEs含量不同,PAEs含量越高的包装材料迁移到食品中的量也越大。结论本研究可以为食品的加工生产、存储、运输过程的安全控制提供理论基础和方法依据。     

纳米二氧化钛改性LDPE薄膜中纳米钛粒子在食品模拟物中的迁移研究

为探究纳米改性LDPE薄膜中纳米钛粒子在食品模拟物中的迁移规律,根据欧盟法规(EU)NO.10/2011,分别采用蒸馏水、3%乙酸溶液(m/V)、10%乙醇溶液(V/V)、95%乙醇溶液(V/V)作为中性、酸性、脂肪性和酒精性食品模拟物,研究在不同温度条件下(40℃和70℃)纳米钛粒子的迁移情况,并研究了微波和紫外处理对迁移结果的影响。研究发现,纳米钛粒子在四种食品模拟物中的迁移量从高到低依次为:酸性食品模拟物、中性食品模拟物、酒精性食品模拟物和脂肪性食品模拟物,并且温度的升高能够促进纳米钛粒子的迁移。纳米钛粒子的迁移量范围为0.0046 mg/kg~0.61 mg/kg。此外,微波处理也能够促进纳米钛粒子的迁移,紫外处理则没有这样的促进作用。根据欧盟规定所允许的最大迁移量5 mg/kg,迁移实验表明纳米二氧化钛改性LDPE薄膜能够作为一种安全的食品包装膜。     

Migration of copper from nanocopper/LDPE composite films

Three nanocopper/low-density polyethylene (LDPE) composite films were tested in food simulants (3% acetic acid and 10% ethanol) and real food matrices (rice vinegar, bottled water and Chinese liquor) to explore the behaviours of copper migration using ICP-OES and GFAAS. The effects of exposure time, temperature, nanocopper concentration and contact media on the release of copper from nanocopper/LDPE composite films were studied. It was shown that the migration of copper into 10% ethanol was much less than that into 3% acetic acid at the same conditions. With the increase of nanocopper concentration, exposure time and temperature, the release of copper increased. Copper migration does not appear to be significant in the case of bottled water and Chinese liquor compared with rice vinegar with a maximum value of 0.54 μg mL^?1 for the CF-0.25# bags at 70°C for 2 h. The presence and morphology of copper nanoparticles in the films and the topographical changes of the films were confirmed by field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM). In this manner, copper nanoparticles of different morphologies, sizes and distribution were found, and samples with higher nanocopper concentration had a more irregular topography. In the case of Fourier transform infrared spectroscopy (FTIR), no chemical bonds formed between copper nanoparticles and LDPE. Copper nanoparticles were just as physically dispersed in LDPE.     

Mobility of alpha-tocopherol and BHT in LDPE in contact with fatty food simulants.

The migration/sorption behaviour of butylated hydroxytoluene (BHT) and alpha-tocopherol was studied in packaging material in contact with fatty food simulants. Two low-density polyethylene (LDPE) films, containing either BHT or alpha-tocopherol as antioxidants, were stored in contact with sunflower oil or 95% (v/v) ethanol. The antioxidant content was monitored in the films throughout a period of 7 weeks. The migration of alpha-tocopherol into the food simulants was slower than that of BHT. Since alpha-tocopherol was transferred from the film to the simulant to a lesser extent, it is considered to be a more stable antioxidant than BHT when used in an LDPE film in contact with 95% ethanol or sunflower oil.     

食品包装污染物双酚类物质在食品模拟体系中的迁移规律研究

采用4 种食品模拟物包括超纯水、30 g/L乙酸水溶液、10%乙醇水溶液和异辛烷对食品金属罐中4 种双酚物（包括双酚A、双酚F、双酚A二缩水甘油醚和双酚F二缩水甘油醚）迁移情况进行研究,并建立半经验的双酚物迁移规律数学模型。结果表明：4 种双酚物同时在10%乙醇溶液中出现最大迁移,且贮存温度和时间对迁移量变化有显著影响。根据模拟实验得到的迁移数据和Fick第二定律建立数学模型,初步确定扩散系数DP,再根据DP估计得到包材的特征参数AP的范围为35.38～48.48。     

Assessment of the migration potential of nanosilver from nanoparticle-coated low-density polyethylene food packaging into food simulants

An experimental nanosilver-coated low-density polyethylene (LDPE) food packaging was incubated with food simulants using a conventional oven and tested for migration according to European Commission Regulation No. 10/2011. The commercial LDPE films were coated using a layer-by-layer (LbL) technique and three levels of silver (Ag) precursor concentration (0.5%, 2% and 5% silver nitrate (AgNO₃), respectively) were used to attach antimicrobial Ag. The experimental migration study conditions (time, temperature and food simulant) under conventional oven heating (10 days at 60°C, 2 h at 70°C, 2 h at 60°C or 10 days at 70°C) were chosen to simulate the worst-case storage period of over 6 months. In addition, migration was quantified under microwave heating. The total Ag migrant levels in the food simulants were quantified by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Mean migration levels obtained by ICP-AES for oven heating were in the range 0.01–1.75 mg l^?1. Migration observed for microwave heating was found to be significantly higher when compared with oven heating for similar temperatures (100°C) and identical exposure times (2 min). In each of the packaging materials and food simulants tested, the presence of nanoparticles (NPs) was confirmed by scanning electron microscopy (SEM). On inspection of the migration observed under conventional oven heating, an important finding was the significant reduction in migration resulting from the increased Ag precursor concentration used to attach Ag on the LDPE LbL-coated films. This observation merits further investigation into the LbL coating process used, as it suggests potential for process modifications to reduce migration. In turn, any reduction in NP migration below regulatory limits could greatly support the antimicrobial silver nanoparticle (AgNP)-LDPE LbL-coated films being used as a food packaging material.     

纳米银-聚乙烯复合包装中助剂对银向食品模拟物迁移的影响

为探究纳米银-聚乙烯复合包装中添加剂对纳米银颗粒向食品模拟物迁移的影响,在20、40 ℃和70 ℃条件下分别将空白纳米银聚乙烯复合包装和含有助剂（抗氧化剂1076、抗氧化剂168、光稳定剂622和光稳定剂944）的纳米银聚乙烯复合包装在3 g/100 mL乙酸溶液和体积分数50%乙醇溶液两种食品模拟物中浸泡1～30 h,然后蒸干定容并用电感耦合等离子体质谱测定银的含量。结果表明：食品模拟物中银的加标回收率在84.19%～115.69%之间,相对标准偏差在3.21%～8.75%之间;在8 h内塑料中的添加剂会促进银向两种食品模拟物的迁移;同时银的迁移率会随着迁移温度的升高和迁移时间的增加而增大直至平衡;平衡时,塑料中的添加剂反而阻碍银向这两种食品模拟物的迁移;银在酸性模拟物中的迁移率大于在酒精类模拟物中的迁移率。     

Alternative fatty food simulants and diffusion kinetics of nylon 12 food packaging.

The migration of laurolactam and cyclic di- and trimer of nylon 12 was assessed using three different films and five food simulants (olive oil, isooctane, 95% ethanol, 50% ethanol, water). Substitute test conditions for migration into olive oil according to European Union Directive EC/97/48 were applied using 95% ethanol and isooctane. Results showed that 95% ethanol overestimated while isooctane underestimated the respective migration into olive oil. Water was the best olive oil substitute, as migration of laurolactam into water and olive oil using the same temperature gave similar results. Additionally, diffusion kinetics of laurolactam were investigated by migration kinetic studies using isooctane and olive oil. Diffusion coefficients determined with isooctane were significantly higher than those found using olive oil. It was proved that isooctane had an interaction and olive oil was inert to the polymer. The diffusion conductance parameter, A(p), for nylon 12 determined using olive oil ranged from 0.3 to 0.6.     

Antioxidant migration resistance of SiOx layer in SiOx/PLA coated film

As novel materials for food contact packaging, inorganic silicon oxide (SiO_x) films are high barrier property materials that have been developed rapidly and have attracted the attention of many manufacturers. For the safe use of SiO_x films for food packaging it is vital to study the interaction between SiO_x layers and food contaminants, as well as the function of a SiO_x barrier layer in antioxidant migration resistance. In this study, we deposited a SiO_x layer on polylactic acid (PLA)-based films to prepare SiO_x/PLA coated films by plasma-enhanced chemical vapour deposition. Additionally, we compared PLA-based films and SiO_x/PLA coated films in terms of the migration of different antioxidants (e.g. t-butylhydroquinone [TBHQ], butylated hydroxyanisole [BHA], and butylated hydroxytoluene [BHT]) via specific migration experiments and then investigated the effects of a SiO_x layer on antioxidant migration under different conditions. The results indicate that antioxidant migration from SiO_x/PLA coated films is similar to that for PLA-based films: with increase of temperature, decrease of food simulant polarity, and increase of single-sided contact time, the antioxidant migration rate and amount in SiO_x/PLA coated films increase. The SiO_x barrier layer significantly reduced the amount of migration of antioxidants with small and similar molecular weights and similar physical and chemical properties, while the degree of migration blocking was not significantly different among the studied antioxidants. However, the migration was affected by temperature and food simulant. Depending on the food simulants considered, the migration amount in SiO_x/PLA coated films was reduced compared with that in PLA-based films by 42–46%, 44–47%, and 44–46% for TBHQ, BHA, and BHT, respectively.