温度对食品级PVC中4种增塑剂迁移量的影响

以食品包装材料聚氯乙烯(PVC)为研究对象,研究PVC中邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)4种增塑剂在30℃～80℃条件下,水、乙酸、乙醇、正己烷4种模拟液中的迁移情况。结果表明,此4种增塑剂都在正己烷的环境下迁移量最大,并且在各种食品模拟液中的迁移量均随温度的升高而增大。     

PVC保鲜膜中增塑剂DOP在水中迁移规律研究

主要研究了不同几种MA条件下3种PVC保鲜膜中增塑剂DOP在蒸馏水中的迁移规律(模拟果蔬MA保鲜的环境),以PE保鲜膜对照。结果表明,3种PVC保鲜膜包装的蒸馏水中增塑剂DOP有不同程度的迁移,而在PE膜包装的水中没有检测到DOP的迁移。PVC保鲜膜DOP的迁移量与温度、时间、保鲜膜DOP的含量、保鲜膜的厚度有一定的相关性。     

食品包装中增塑剂DEHP的迁移风险分析

模拟日常使用的情况设计试验条件,研究食品包装材料中邻苯二甲酸二(2-乙基己)酯(DEHP)迁移到食品中的风险规律。试验结果表明:DEHP增塑剂的迁出量随着迁移时间的增加而增加,180min以后迁出量趋于稳定;40℃下迁移出的增塑剂的量比4℃和20℃下大大增加;与橄榄油相比,正己烷是一种较苛刻的迁移模拟物,同等条件下迁入正己烷中的增塑剂要比迁入橄榄油中的多;迁移过程的振荡也会大大提高迁移效率。     

食品塑料袋中DEHP气相色谱检测方法的建立

DEHP是塑料中常用的增塑剂之一,直接与内装高脂食品接触时,能够从塑料中迁移到内装食品中,造成内装食品的污染。DEHP对人体系统有不良影响,具有致畸、致癌的作用。本实验对各种材质(PVC、PE、PP、PS等)的食品塑料袋中DEHP的测定进行了较为系统的研究,采用气相色谱法,FID检测器,对DEHP进行测定。本方法检出限为3.38×10-3mg/kg,加标回收率为90.7%～105.1%,能够满足各种材质食品塑料袋中低浓度至高浓度DEHP含量测定的需要。     

聚乳酸抗菌包装中麝香草酚在食品模拟物中迁移规律

研究麝香草酚/聚乳酸包装材料中的抗菌剂麝香草酚在食品模拟物中的迁移行为。在4、10、20、30 ℃条件 下分别将麝香草酚/聚乳酸包装材料浸入蒸馏水溶液、体积分数4%乙酸溶液、正己烷溶液、体积分数10%乙醇溶液 中,通过紫外分光光度法测定食品模拟液中麝香草酚迁移量,分析温度和食品模拟物对麝香草酚迁移量的影响,在 实验数据基础上,采用Piringer方程建立麝香草酚迁移模型,分析验证迁移模型的合理性。结果表明：麝香草酚迁 移量随着迁移温度升高和迁移时间延长而逐渐上升直至平衡,且在4 种食品模拟物中麝香草酚的迁移量大小顺序为： 正己烷＞10%乙醇＞4%乙酸＞蒸馏水;根据幂律方程发现麝香草酚的迁移机制符合Fick扩散定律,且迁移方程扩散系 数随迁移温度升高而增大,分配系数与之相反;Piringer方程能够较好地描述麝香草酚迁移行为。在迁移实验的基础 上构建数学模型,进一步完善基于聚乳酸食品包装材料的迁移理论,以期更好地预测食品包装中麝香草酚的迁移。     

食品接触材料PVC中塑化剂迁移规律研究及迁移模型建立

运用同位素内标稀释结合气相色谱质谱方法检测PVC中的塑化剂DIBP、DBP、 DEHP和DEHA。以3 %乙酸、10 %、20 %、50 %、95 %乙醇作为食品模拟溶液,在25 ℃及40 ℃条件下对PVC中四种塑化剂的迁移情况进行研究。另外以Fick第二扩散定律为依据建立PVC中塑化剂的迁移规律数学模型。同时评价模型的可行性,从而提供有效的食品安全性评价。     

黄酒包装容器材料中邻苯二甲酸酯的迁移研究

考察常用黄酒包装容器材料中邻苯二甲酸酯类化合物的含量及分布情况,选取玻璃瓶盖中PVC塑料垫片来浸泡黄酒,探究邻苯二甲酸酯类化合物的迁移溶出量随模拟浸泡时间和浸泡温度的变化情况。结果表明,DBP、DINP、DEHP从PVC塑料垫片中溶出到黄酒中的迁移量随浸泡时间、浸泡温度的增加总体上呈逐渐增长趋势;尤其在95℃高温条件下,15 min后,DBP的迁移量急剧增加,随着时间延长至120 min,迁移量缓缓增加,DINP、DEHP迁移量的变化情况相似,但是增长幅度较小,表明95℃高温对塑化剂DBP的溶出影响很大。     

饼干加工过程中6种邻苯二甲酸酯类增塑剂迁移规律研究

饼干制品中常有增塑剂检出,有效的控制措施是防止饼干制品中增塑剂污染的关键。本文针对饼干加工工艺中涉及塑料制品的加工环节,采用特制的含6种增塑剂的PVC膜对饼干加工过程中增塑剂迁移规律进行研究。结果表明:接触时间和温度是增塑剂发生迁移的主要影响因素;随着接触时间的增加,6种增塑剂的迁移量随之增加,特别是高温的饼胚,增塑剂可在短时间内快速迁入。DINP和DIDP的迁移速率高于DBP、BBP、DEHP和DNOP。在饼干加工的各个环节,原料或成品与含增塑剂的平台、容器或包装物接触均可导致增塑剂向饼干中的迁移。其中长时间的包装物接触是增塑剂迁移的主要因素。     

气调包装及天然保鲜剂对冷却鲜猪肉的保鲜效果研究

对冷却鲜猪肉分别用保鲜剂(含乳酸钠5%、异维生素C钠0.2%和乙酸0.4%的混合保鲜溶液)处理加PE塑料袋包装、PE/PA塑料袋气调包装(25% CO2、25% N2和50% O2混合气体)和保鲜剂处理加PE/PA塑料袋气调包装,与PE塑料袋包装对照,研究其在0～4℃冷却保存条件下不同处理方法的保鲜效果。每隔2d对猪肉进行感官评定、测定其TVB-N值、菌落总数,并进行球蛋白沉淀试验,以判定猪肉新鲜度的变化。结果表明:PE/PA塑料袋气调包装和保鲜剂处理均明显延长冷却鲜猪肉的保存期,可使其保存期分别达到12d和9d;两者同时应用效果更好,可使冷却鲜猪肉的保存期达到15d以上;气调包装的冷却保存猪肉颜色始终保持鲜红状态;课题组自主设计、制造的气体比例混合器,用于冷却肉的气调包装,保鲜效果优良。     

小波变换辅助的塑料膜增塑剂含量气相色谱-质谱同时测定

以正己烷为提取剂采用均质-超声法提取PVC塑料膜中的增塑剂,以气相色谱-质谱法(GC-MS)同时测定9种增塑剂含量,其中邻苯二甲酸二异壬酯(DINP)和邻苯二甲酸二异癸酯(DIDP)2种增塑剂的总离子流图所对应的色谱峰重叠严重,利用连续小波变换(CWT)对重叠严重的色谱峰进行解析,结果其色谱峰得到良好分离.CWT辅助解析重叠色谱的均质-超声提取GC-MS法为PVC膜中多种增塑剂同时测定提供了新途径.     

2018年吉林省部分地区市售食用植物油产品中塑化剂含量的检测结果分析

目的 了解2018年吉林省部分地区食用植物油产品中塑化剂的污染情况。方法 检测并分析食用植物油产品155批次, 依据GB 5009.271-2016《食品安全国家标准 食品中邻苯二甲酸酯的测定》(第二法 气相色谱-质谱法 外标法), 对产品中的邻苯二甲酸二丁酯(dibutyl phthalate, DBP)和邻苯二甲酸二(2-乙基)己酯(di(2-ethylhexyl) phthalate, DEHP)2项塑化剂指标进行含量检测。结果 共有18批次食用植物油产品的塑化剂检测结果高于参考限值, 其中DBP超限率为11.61%, DEHP超限率为0.65%。结论 本次检测的食用植物油产品出现一定的塑化剂问题, DBP污染较为明显。污染来源可能来自塑料包装物、加工环节及环境污染, 塑化剂迁移途径和预防控制问题需要引起相关部门的重视。     

Reduced migration from flexible poly(vinyl chloride) of a plasticizer containing beta-cyclodextrin derivative

The migration of endocrine-disrupting di-(2-ethylhexyl) phthalate (DEHP) poses a serious threat to public health and the environment. In this study, we successfully prepared a plasticizerwith reduced DEHP migration by directly incorporating 2,3,6-per-O-benzoyl-beta-cyclodextrin (Bz-beta-CD) into DEHP. Bz-beta-CD was prepared by esterification between the hydroxyl groups of beta-CD and benzoyl chloride. The presence of this cyclodextrin is expected to facilitate formation of stable complexes through pi-pi association with DEHP molecules. The flexible PVC was prepared with a gelation-fusion process that uses the prepared migration-resistant plasticizer, and its properties (flexibility, thermal stability, and clarity) were evaluated by carrying out DSC and tensile testing, TGA, and haze testing, respectively. No significant changes in the physical properties of the flexible PVC were observed when Bz-beta-CD was added. DEHP migration tests were carried out for the flexible PVC according to the ISO 3826:1993(E) test method, and the quantity of migrated DEHP was then determined with UV-vis spectroscopy. It was found that the addition of Bz-beta-CD decreases the levels of DEHP migration from the flexible PVC samples by almost 40%. We investigated the molecular interaction between Bz-beta-CD and DEHP using molecular mechanics simulations, and we conclude that this reduction in DEHP migration is due to the formation of stabilized pi-pi attractive association and inclusion complexes of Bz-beta-CD and DEHP in flexible PVC.     

Hyperbranched poly(epsilon-caprolactone) as a nonmigrating alternative plasticizer for phthalates in flexible PVC

Hyperbranched (dendritic) poly(epsilon-caprolactone)s (HPCLs) were synthesized to have architectural variations, which are the different lengths of linear segments and different numbers of branches, and were used as plasticizers for flexible poly(vinyl chloride) (PVC). The plasticization efficiency estimated by the lowering of glass transition temperature and the enhancement in ultimate elongation indicated that the HPCLs with the shorter linear segments and the larger number of branches imparted as high flexibility as di(ethylhexyl) phthalate (DEHP) and much higher flexibility than their linear analogue, linear poly(epsilon-caprolactone), which is one of currently used polymer plasticizers. Volatility, extractability, and exudation tests for PVC/HPCL samples showed that there was no plasticizer migration even at very harsh condition, while ca. 7-78% of additives in PVC/DEHP was migrated out of samples, indicating that the HPCL can be used as an alternative plasticizer to remove the potential health risk from migrating phthalates during end use.     

啤酒中邻苯二甲酸酯检测方法优化及迁移量研究

该试验建立了顶空固相微萃取-气质联用法（HS-SPME-GC/MS）分析啤酒中塑化剂邻苯二甲酸酯（PAEs）的测定方法,采用单点标准加入法测定了6种市售啤酒以及在3种迁移试验条件下瓶盖内垫片在啤酒和模拟物（体积分数为10%乙醇溶液）中PAEs的迁移量。啤酒样品采用50 μm聚二乙烯基苯/碳分子筛/聚二甲基硅氧（DVB/CAR/PDMS）萃取头萃取,在55 ℃水浴保温60 min,该方法共定量了16种PAEs的组分。结果表明,通过对啤酒PAEs的检测,发现使用PVC内垫片和PE内垫片的啤酒中DBP的迁移量均为最高,分别为9.48 μg/L与8.26 μg/L,而DIBP、DEHP则迁移量较低,但DEHP在体积分数为10%的乙醇溶液中含量较高。通过试验可知温度及时间是啤酒中PAEs增加的一个重要因素,应严格禁止将啤酒横放、倒放或高温储存,避免酒液接触内垫片。     

Migration of di-(2-ethylhexyl) phthalate from PVC child articles into saliva and saliva simulant.

A simple migration test and a more complicated simulation of children's sucking and biting was used to establish migration of DEHP from PVC child-use articles into saliva and compared to a mimic test. The static migration test of a film containing approximately 30% DEHP with saliva simulant gave the lowest values of DEHP; simple shaking increased the amounts of DEHP from 25 +/- 8 to 499 +/- 153 micrograms/g film. The more complicated arrangements to simulate sucking and biting are not so suitable for standard applications. When comparing the in vitro migration tests with the mimic test the factors were 25 and 29 for the static tests (3 and 6 hours) and 1.4 for the shaking test.     

Migration from plasticized films into foods. 5. Identification of individual species in a polymeric plasticizer and their migration into foods.

To assess the significance of migration of polymeric plasticizers into foods, chemical characterization and quantification of individual oligomeric species is required. This paper reports the identification of seven individual oligomers isolated from a poly(butylene adipate) plasticizer. Based on mass spectrometry, NMR and chemical degradation, the oligomers were identified as a series of diol-terminated units ranging from a trimer up to an 11-monomer unit, along with a cyclic tetramer, all in the molecular weight range of 300-1100. A study of the migration of polymeric plasticizer from PVC film into olive oil indicated preferential migration of low molecular weight species. These oligomers which comprised 24% of the parent plasticizer contributed more than 90% of the plasticizer migration with the smallest oligomers migrating 90-fold more readily than the bulk of the plasticizer. From a knowledge of total polymeric plasticizer migration from PVC films under actual conditions of food-use, the abundance of individual oligomers in the foods has been estimated.     

纸包装油墨中增塑剂向奶粉的迁移

纸包装油墨中含有有毒有害物质并可通过包装材料迁移进入内装食品从而危害人体健康。模拟实际印刷条件制作真实油墨迁移单元,研究纸张胶印油墨中4种主要增塑剂（3种邻苯二甲酸酯类增塑剂和近年流行的环保增塑剂乙酰基柠檬酸三丁酯）向奶粉的迁移,考察其在100、70、50、25 ℃的迁移行为,探讨增塑剂的性质及其在纸张中的分布等因素对迁移行为的影响。结果表明：4种增塑剂的最大迁移率在6.7%～67.8%之间。纸包装油墨中增塑剂的迁移防护性能还有待提高。     

A simple and reproducible testing method for dialkyl phthalate migration from polyvinyl chloride products into saliva simulant

We describe a method of mechanical agitation to determine rates of dialkyl phthalate migration from polyvinyl chloride (PVC) products into saliva simulant. The method consists of rotary shaking of a sample with 30 mL of saliva simulant (pH 7.0) at 35 degrees C in a 50 mL glass tube at 300 rpm for 15 min, then measuring the amount of dialkyl phthalate in the saliva simulant by HPLC with a UV detector. The migration rates of diisononyl phthalate (DINP), di-2-ethylhexyl phthalate (DEHP) and di-n-butyl phthalate (DBP) from PVC plates containing about 45% (w/w) plasticizer (molded in our laboratory) were identical. However, the migration rates from molded plates containing 13% (w/w) DBP were almost double those of DINP and DEHP at the same ratios. In addition, the amounts of DINP that migrated in vitro after rotary shaking for 15 min were equivalent to those in vivo determined in saliva from volunteers who chewed plates for 60 min. The migration rates of dialkyl phthalates from 11 commercially available toys ranged from 15.6 to 85.2 micrograms/cm2/h [relative standard deviation (RSD), 3 to 12%].     

食品模拟体系中淀粉基膜材增塑剂的迁移

本文采用酯化淀粉以三乙酸甘油酯为增塑剂,经流延法制备了酯化淀粉薄膜,并利用傅里叶红外光谱衰减全反射技术(ATR-FTIR)和热重分析仪(TGA)分析了淀粉基膜材与不同食品模拟体系接触后其表层增塑剂和整体增塑剂的变化情况。结果表明,基于与淀粉基膜材、增塑剂之间的亲和性差异,食品模拟体系对淀粉基膜材产生不同的溶胀作用,导致不同程度的增塑剂迁移;与淀粉基膜材亲和性越高的食品模拟体系,对淀粉基膜材表层和内部的溶胀更迅速,并可溶解更多的增塑剂分子,从而导致淀粉基膜材中更大程度的增塑剂迁移;表层增塑剂和整体增塑剂的迁移情况差异表明,溶剂溶胀和增塑剂迁移由膜材表层向内部发生。基于以上结果可推断,在实际应用过程中,选择合适的应用领域、设计调整材料结构可主动抑制增塑剂迁移,实现这类新型包装材料的安全使用。