植物纤维食品接触材料中邻苯二甲酸酯类增塑剂的研究现状

从迁移条件与检测方法两个方面介绍了近年来国内外学者关于植物纤维食品接触材料中邻苯二甲酸酯类(Phthalic Acid Easters,PAEs)增塑剂的研究现状,选择合适的迁移实验条件并建立高灵敏度、低检出限的检测方法是近年来相关学者在研究中的工作重点,但仍有待于深入开展。同时该方面研究还证实了植物纤维食品接触材料中PAEs类增塑剂的存在并且危害消费者健康,对我国相关生产企业具有警示作用,也为国家尽快发布植物纤维类食品接触材料中增塑剂限量或特定迁移限量,并制定相关迁移实验与检测方法的法规标准提供参考依据。     

气相色谱与气相色谱-质谱法用于食品增塑剂检测中的结果分析

食品增塑剂作为高分子材料助剂,增塑剂在环境雌激素中属于酞酸酯类物质,增塑剂被广泛应用在工业生产中,不可食用,也不能增添在食品中。若人体误摄入增塑剂,将危害人体生殖系统和人体内分泌系统。鉴于增塑剂对人体的危害,本文旨在研究采用气相色谱与气相色谱-质谱法检测食品中增塑剂的可行性,并对结果进行分析。     

复合增塑剂对大豆分离蛋白可生物降解材料性能影响的研究

本文利用水、甘油和己内酰胺作为复合增塑剂增塑PEG400改性SPI降解材料,以材料的拉伸强度、断裂伸长率及透光率作为考察目标,并利用DSC研究了增塑剂对SPI材料的Tg的影响。研究发现：材料经复合增塑剂增塑后,材料的性能有了很大的提高,测得材料的最大拉伸强度为：17．9MPa、断裂伸长率353．7％、透光率为40．6％。     

食品包装材料中柠檬酸酯类增塑剂GC/MS/SIM分析

为研究食品包装材料中柠檬酸酯类增塑剂的含量,采用超声辅助二氯甲烷萃取,GC/MS/SIM的检测方式,建立食品包装材料中柠檬酸酯类增塑剂含量的检测方法。结果表明,柠檬酸酯类增塑剂含量在0.001~0.1 mg/mL范围内呈良好线性,线性相关系数R~20.99,检出限范围为0.061~0.066μg/g。2种柠檬酸酯类增塑剂的平均回收率为91.46%~107.73%,RSD为1.69%~4.73%(n=6)。运用该方法检测26种食品包装材料,仅有4种包装材料中存在柠檬酸三丁酯和乙酰柠檬酸三丁酯2种增塑剂。     

食品塑料包装中邻苯二甲酸酯类增塑剂的调查分析

对市场上常见食品塑料包装材料中邻苯二甲酸酯类增塑剂的使用情况进行了抽样调查,采用固相萃取-气相色谱法检测增塑剂。结果表明:13个样品中PAEs化合物总量在41.30～16563.05 mg/kg之间,所有样品中均含有增塑剂DEHP,5个样品还含有DBP。DBP含量均超过3.0 mg/kg,最高含量16016.98 mg/kg,DEHP含量均超过1.5 mg/kg,DEHP最高含量达到15200.78 mg/kg。最后对我国增塑剂问题现状控制和修订相应国家标准提出了建议。     

淀粉浆料用极性增塑剂及其增塑作用的研究进展

为提高淀粉的上浆性能,分析了淀粉浆料经纱上浆中使用极性增塑剂的意义,阐述了极性增塑剂对淀粉浆料的增塑作用机制,论述了极性增塑剂对淀粉浆料的增塑效果,包括对其浆膜力学性能、黏附性能及其与聚乙烯醇的相分离速度,总结了极性增塑剂在淀粉浆料上浆中应用的研究现状,并对今后淀粉浆料用极性增塑剂的研究方向进行了预测。认为复合极性增塑剂增塑效果研究和采用新方法合成新品种的极性增塑剂,将是今后淀粉经纱上浆用极性增塑剂的重要研究方向。     

直链淀粉/支链淀粉比例对酯化淀粉薄膜增塑剂迁移的影响

通过选择不同直链淀粉/支链淀粉比例的酯化淀粉,制备了不同结构特征的淀粉基薄膜,并对这些结构对抑制增塑剂邻苯二甲酸二乙酯(DEP)在微波条件下迁移的影响进行了研究。结果表明,直链淀粉/支链淀粉比例为零的waxy酯化淀粉薄膜材料中分子间相互作用力强,有序微区尺寸较大,抑制DEP迁移的程度最大。直链淀粉/支链淀粉比例为50%的G50酯化淀粉薄膜材料中,分子间相互作用力虽弱,但较大的有序微区及内部致密的结构起到了较好地限制增塑剂迁移的作用。直链淀粉/支链淀粉比例为80%的G80酯化淀粉薄膜材料中虽微晶存在,但分子间相互作用力较弱、有序微区尺寸小、增塑剂迁移量最大。因此,可以通过改变直链淀粉与支链淀粉的比例来降低酯化淀粉薄膜中增塑剂的迁移,为更好地合理设计及安全使用淀粉基薄膜材料提供了基础数据及理论依据。     

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。     

食品接触制品中邻苯二甲酸酯类增塑剂的风险评估

邻苯二甲酸酯类物质作为增塑剂,广泛应用于食品接触材料及制品的生产,其安全性是消费者密切关注的问题。从危害性描述、危害作用与剂量、暴露评估及风险描述等方面对邻苯二甲酸酯类物质的使用进行风险评估,结果表明:人体暴露于邻苯二甲酸酯类增塑剂的剂量已构成消费者健康风险,应限制邻苯二甲酸酯类物质在食品接触材料中使用,建议开发环保新型增塑剂作为替代品。     

纺织品印花热固油墨配方的改进及制备方法

<正>热固油墨在印花行业中的应用越来越广泛,越来越多的运动品牌服饰与休闲服饰都采用热固油墨进行印花,其在印花材料市场占有率也不断提升。热固油墨主要是由树脂、增塑剂、助剂、颜料组成,与普通网版印刷油墨不同的是其配方中含有大量的增塑剂,且不含任何水和溶剂。邻苯二甲酸酯为最常用的增塑剂的一种,而研究表     

浓香型原酒中塑化剂的吸附剂筛选

选用4种大孔树脂和4种酒类专用活性炭为吸附剂,采用静态吸附法,首先对57%酒精度模拟加标酒样进行吸附实验,以邻苯二甲酸二甲酯(dimethyl phthalate,DMP)、邻苯二甲酸二异丁酯(diisobutyl phthalate,DIBP)、邻苯二甲酸二丁酯(di-n-butyl phthalate,DBP)、邻苯二甲酸二(2-乙基)己酯(diethylhexyl phthalate,DEHP)4种邻苯二甲酸酯类塑化剂的吸附率为指标进行初选。之后用57%酒精度浓香型原酒进行验证,以塑化剂的吸附率和原酒中己酸乙酯、乙酸乙酯、乳酸乙酯、丁酸乙酯4种香气成分的损失率作为指标,筛选出理想的吸附剂。结果表明:1)JT201、JT203酒类专用活性炭对模拟酒样中4种塑化剂的吸附效果较好,平均吸附率为91.01%和87.21%,大孔树脂中非极性的D4006较其他树脂吸附效果好,吸附率达73.67%;极性大孔树脂NKA-Ⅱ和颗粒活性炭的吸附率不足60%,初选JT201、JT203酒类专用活性炭为原酒中塑化剂的吸附剂。2)JT201、JT203酒类专用活性炭吸附后,原酒中DMP、DBP的去除率均达90%以上,JT201对DIBP、DEHP的去除率均达80%以上,JT203对DIBP、DEHP去除率为78%、72%;JT201、JT203吸附处理后原酒中己酸乙酯、乙酸乙酯、乳酸乙酯、丁酸乙酯分别损失7.7%、6.1%、11.9%、11.6%和10.4%、8.6%、33.9%、16.0%,本研究确定JT201酒类专用活性炭为去除浓香型原酒中塑化剂的最佳吸附剂。     

食品及食品包装材料中塑化剂的检测研究进展

食品和食品包装材料中塑化剂对人体的危害不可小觑。本文主要介绍了食品及食品包装材料中塑化剂国内外检测标准、样品前处理方法及主要的检测方法。欧盟法规(EU)No 10/2011相对于以往的2002/72/EC对于迁移测试的要求整体趋于严格,生产企业有必要改进生产工艺以应对更新的测试规则。国家现有的标准中对于食品和食品包装材料中塑化剂有一定的要求,目前最常见的研究大部分为食品和食品包装材料中邻苯二甲酸酯类化合物,但对于其他类型的塑化剂检测结果相对较少,这也将是今后食品和食品包装材料中塑化剂检测研究的一个主要方向。     

Identification of unknown substances in polyvinyl chloride gloves containing non-phthalate plasticizers

The use of polyvinyl chloride gloves containing di(2-ethylhexyl) phthalate for food contact applications is restricted. In their place, polyvinyl chloride gloves containing non-phthalate plasticizers (PVC-NP) have been introduced. They contained unknown substances, so they were studied by GC/MS, HR-MS and NMR. The chemical structures of the unknown substances were confirmed to be diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate, and alkylsulfonic acid phenyl ester, which are plasticizers. Including di-isononyl adipate, the contents of the plasticizers were 37.5-48.9% in the PVC-NP gloves, and their migration levels were 1,010-1,390 ppm into n-heptane. These are very high levels. These plasticizers are not widely used for food contact polyvinyl chloride throughout the world, and they have also not been registered as self-standards by Japanese manufacturers. Careful consideration will be necessary for the selection of a suitable plasticizer substitute.     

Survey of plasticizers in polyvinyl chloride toys

Plasticizers in 101 samples of polyvinyl chloride (PVC) toys on the Japanese market were surveyed. No phthalates were detected in designated toys, though bis(2-ethylhexyl)phthalate, diisononyl phthalate, diisobutyl phthalate, dibutyl phthalate, diisodecyl phthalate and benzyl butyl phthalate were detected in more than half of other toys. 2,2,4-Tributyl-1,3-pentanediol diisobutylate, o-acetyl tributyl citrate, adipates and diacetyl lauroyl glycerol, which are alternative plasticizers to phthalates, were detected. The results of structural analysis confirmed the presence of di(2-ethylhexyl)terephthalate, tributyl citrate, diisononyl 1,2-cyclohexanedicarboxylate and neopentyl glycol esters; these have not previonsly been reported in Japan. There appears to be a shift in plasticizers used for designated toys from phthalates to new plasticizers, and the number of different plasticizers is increasing.     

不同塑化剂对柠檬酸淀粉酯成膜性能的影响

以甘油、乙二醇、山梨醇和壳聚糖为塑化剂,机械活化柠檬酸淀粉酯为原料,以断裂伸长率为评价指标,通过SEM、FT-IR、TGA和接触角的分析,探讨不同塑化剂对淀粉酯成膜性能的影响。结果表明,不同塑化剂对淀粉酯的影响不同。不同塑化剂对淀粉酯膜的断裂伸长率影响为甘油>山梨醇>乙二醇>壳聚糖>原淀粉。添加塑化剂能使淀粉酯更好地成膜。SEM分析表明,以甘油和壳聚糖为塑化剂的淀粉酯膜具有更多网状结构,表面透气性好;以乙二醇和山梨醇为塑化剂的淀粉酯膜更为致密,表面相对光滑,气密性更好。FT-IR表明,淀粉酯膜均成功塑化且具有相同峰型,说明不同塑化剂的塑化机理基本相同。TGA显示,热分解温度与塑化剂分子大小及羟基含量存在密切关系。接触角分析表明,不同塑化剂对于淀粉酯膜的亲水性各不相同,其亲水性大小为山梨醇>甘油>壳聚糖>乙二醇。     

O17. The development of 'time release' nail enamels

In our recent studies on the effects of plasticizers on nail enamel films, we developed a high interest in a phenomenon that we named as 'internal flow'[1]. During the film forming process there is an area that develops beneath the film surface where the film components remain dynamic and mobile. The time frame during which the film maintains this status is directly related to the balance of the resins, plasticizers, polymers and solvents utilized. We found that the longer this 'internal flow' persists, the better the nail enamel wears. At Tevco, we have been able to control the rate at which the solvents and plasticizers flash off the substrate during the film forming process by regulating the interactions and the levels of film constituents. This 'time release' action is the foundation of our study. This study shows that the alkyl adipates are an integral component in controlling the film's internal flow through time release. As plasticizers, these materials, when in proper balance with other components, can create a film surface that is crack-and scuff-resistant. Finally, the substrate in this study is the human nail. The film we developed has to adhere and provide consistent performance over a wide range of temperatures, oil content and the surface abrasion of human nails. We have found that by utilizing adhesion promoters in conjunction with our optimized internal flow time release formula, our film meets all required criteria and generally outperforms conventional quick dry films. In conclusion, we have been able to optimize the film characteristics of conventional quick dry nail enamels. By controlling the internal flow of the film, we can enhance the performance criteria generally expected by consumers in nail enamels.     

同位素稀释三重串联四级杆质谱法测定饮用水中4种增塑剂

目的建立同位素稀释-气相色谱-三重四级杆质谱法同时测定饮用水中3种邻苯二甲酸酯和己二酸二(2乙基己基)酯的方法。方法样品采用正己烷提取后,气相色谱三重四极杆质谱检测,内标法定量。结果方法具有良好线性,相关系数R均大于0.998,定量限为0.1~0.5 g/L。各组分平均回收率为92.3%~105.3%,相对标准偏差为0.4%~5.5%。实际样品中3种增塑剂有检出。结论该方法操作简单,准确度和灵敏度高,重现性好,可作为生活饮用水中增塑剂含量检测的确证方法。     

THE EFFECTS of PLASTICIZERS ON CRYSTALLINITY, PERMEABILITY, and MECHANICAL PROPERTIES of METHYLCELLULOSE FILMS

The effects of plasticizers (polyethylene glycols [PEG] 400, 1,450, 8,000 and 20,000, glycerol [G] and propylene glycol [PG]), 30% dry basis, on the physical properties of methylcellulose (MC) films were investigated. With the exception of PG, plasticizers with low molecular weights (G and PEG 400) caused the largest increase in the d₁₀₁ spacing of the crystal lattice. All plasticizers significantly (α= 0.05) increased oxygen (O₂P) and water vapor permeabilities (WVP) of the films as compared to that of unplasticized MC, with PEG 400 having the greatest effect on O₂P and G having the greatest effect on WVP. With the exception of PG, all plasticizers decreased the tensile strength of MC films, with PEG 400 causing the largest decrease. With the exception of PG and PEG 400, all plasticizers increased percent elongation values of MC films, with PEG 1,450 having the greatest effect. Glycerol and PEG were the most effective plasticizers for MC. the higher molecular weight plasticizers do provide some plasticizing properties and may be more suitable for applications that require a lower permeability to water vapor than can be achieved with glycerol.     

气相色谱-串联质谱法测定涂布纸中邻苯二甲酸酯类增塑剂

以丙酮为萃取溶剂,采用微波辅助萃取技术提取涂布纸中的邻苯二甲酸酯类增塑剂,提取产物进行气相色谱-串联质谱法（GC-MS）测定,从而建立了一种同时测定涂布纸中多种邻苯二甲酸酯类增塑剂的快速检测方法。该方法的精密度（RSD）均小于14%,加标平均回收率为83.6%～104.1%。在信噪比为10（S/N=10）的条件下,DINP、DIDP和DMPP的定量下限分别为0.2、0.2、0.1 mg/kg,其余各组分的定量下限均小于0.05 mg/kg。采用该方法对市售涂布纸进行测定,结果在部分涂布纸中检出多种邻苯二甲酸酯类增塑剂。