影响聚丙烯塑料中抗氧剂BHT向食品中迁移规律因素研究
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摘要
目的为降低食品包装材料对食品的污染风险,研究影响2,6-二叔丁基-4-甲基苯酚(butylated hydroxytoluene,BHT)向食品中迁移规律的因素并有效预测迁移量。方法研究了含BHT的聚丙烯母料的比表面积和模拟液的溶解度参数对BHT向模拟液中迁移规律的影响,并把Scatchard-Hilderbrand热力学理论模型预测平衡分配系数(D_(r0))与实验值(D_r)进行比较分析。结果模拟中BHT的浓度(C_t)与浸泡时间(t)符合C_t=a×(1-e~(-b×t))方程式,且塑料比表面积越大,迁移速率和迁移平衡分配系数(模拟液/塑料)越大;平衡分配系数(D_r)与比表面积(S)符合方程lnD_r=-2.944+2.157e~(-53.6S),平衡分配系数实验值与Scatchard-Hilderbrand热力学理论模型计算值随模拟液的溶解度参数变化趋势基本一致,实验值与计算值的比值随模拟液与聚丙烯的溶解度参数差值减小而增大。结论塑料的比表面积和模拟液的极性对Scatchard-Hilderbrand热力学理论预测聚丙烯中BHT向模拟液中迁移平衡分配系数有一定的影响,在向溶解度参数为7.0~13.0(cal/cm~3)~0.5范围内的模拟液中平衡分配系数的预测均有良好的适用性。
Objective To study the factors affecting the migration of butylated hydroxytoluene(BHT) into food and predict the migration, in order to reduce the risk of food packaging materials to food contamination MethodInfluence of specific surface area of polypropylene(PP) masterbatch containing BHT antioxidants and solubility parameter of food stimulant on migration regulation of BHT antioxidants from polypropylene plastics to food stimulant was investigated, balance partition coefficient value(D_(r0) )were predicted with Scatchard-Hilderbrand thermodynamic model and was contrasted with experiment one(D_r). Results The relation of BHT Antioxidants concentration(C_t) in food stimulant with immersion time(t) followed the equation: C_t=a(1-e~(-b×t)), the larger the specific surfacearea was, the larger the migration rate and balance partition coefficient value were. Relation of balance partition coefficient value(D_r) with specific surface area of polypropylene(S) followed the equation: lnD_r=-2.944 +2.157 e~(-53.6 S). Experiment value was consistent with Scatchard-Hilderbrand thermodynamic calculating value in variation trend of balance partition coefficient with solubility parameter of stimulants. The ratio of the experimental value to the calculated value increased with the decrease of the solubility parameter difference between the simulated solution and the polypropylene. Conclusion Balance partition coefficient value(D_(r0))of BHT migration from PP into stimulants predicted with Scatchard-Hilderbrand thermodynamic model is influenced by specific surface area of polypropylene(S) and solubility parameter of food stimulant. Scatchard-Hilderbrand thermodynamic model is suitable for prediction of balance partition coefficient of BHT migration from PP into stimulants with 7.0~13.0(cal/cm3)~(0.5 )solubility parameter.
Objective To study the factors affecting the migration of butylated hydroxytoluene(BHT) into food and predict the migration, in order to reduce the risk of food packaging materials to food contamination MethodInfluence of specific surface area of polypropylene(PP) masterbatch containing BHT antioxidants and solubility parameter of food stimulant on migration regulation of BHT antioxidants from polypropylene plastics to food stimulant was investigated, balance partition coefficient value(D_(r0) )were predicted with Scatchard-Hilderbrand thermodynamic model and was contrasted with experiment one(D_r). Results The relation of BHT Antioxidants concentration(C_t) in food stimulant with immersion time(t) followed the equation: C_t=a(1-e~(-b×t)), the larger the specific surfacearea was, the larger the migration rate and balance partition coefficient value were. Relation of balance partition coefficient value(D_r) with specific surface area of polypropylene(S) followed the equation: lnD_r=-2.944 +2.157 e~(-53.6 S). Experiment value was consistent with Scatchard-Hilderbrand thermodynamic calculating value in variation trend of balance partition coefficient with solubility parameter of stimulants. The ratio of the experimental value to the calculated value increased with the decrease of the solubility parameter difference between the simulated solution and the polypropylene. Conclusion Balance partition coefficient value(D_(r0))of BHT migration from PP into stimulants predicted with Scatchard-Hilderbrand thermodynamic model is influenced by specific surface area of polypropylene(S) and solubility parameter of food stimulant. Scatchard-Hilderbrand thermodynamic model is suitable for prediction of balance partition coefficient of BHT migration from PP into stimulants with 7.0~13.0(cal/cm3)~(0.5 )solubility parameter.
引文
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[15]李敏雯,肖少军,张钦发.Scatchard-Hildebrand热力学模型在预测PE中有害物质迁移分配系数的应用[J].食品工业科技,2016,37(5):121-125.Li MW,Xiao SJ,Zhang QF,et al.Application of predicting migration partition coefficient of harmful migrantsin PE by Scatchard-Hildebrand thermodynamic modeling[J].Sci Technol Food Ind,2016,37(5):121-125.
[16]张艳,张钦发,肖少军,等.影响Scathard-Hildebrand统计热力学理论预测PVC中增塑剂迁移平衡分配系数的因素[J].食品工业科技,2016,37(17):138-141.Zhang Y,Zhang QF,Xiao SJ,et al.Influencing factors of predicting migration partion coefficient ofplasticizers in PVC by Scatchard-Hildebrand thermodynamic model[J].Sci Technol Food Ind,2016,37(17):138-141.
[17]Elmira AT,Frantz F,Stéphane D.Simple method to calculate partition coefficient of migrant in food stimulant/polymer system[J].J Food Eng,2005,77(1):135-139.
[18]李以圭.金属溶剂萃取热力学[M].北京:清华大学出版社,1988.Li YG.Metal solvent extraction thermodynamics[M].Beijing:Tsinghua University Press,1988.
[2]秦蓓.塑料食品包装材料安全性研究现状[J].包装工程,2011,32(19):33-35.Qin B.Progress of plastic food packaging safety research[J].Packag Eng,2011,32(19):33-35.
[3]王成涛.塑料食品包装材料的化学物迁移与危害[J].北京工商大学学报(自然科学版),2011,29(5):8-9.Wang CT.Chemical migration and harm of plastic food packaging materials[J].J Beijing Technol Bus Univ(Nat Sci Ed),2011,29(5):8-9.
[4]汪仕韬,邵卫卫,薛娜娜,等.食品塑料包装材料危害物安全风险分析[J].塑料包装,2015,25(6):41-43.Wang ST,Shao WW,Xue NN,et al.Safety risk analysis of harmful substances in food plastic packaging materials[J].Plast Packag,2015,25(6):41-43.
[5]黎盛,徐丹,徐毅,等.塑料食品包装的安全性分析[J].食品工业科技,2011,32(12):391-393.Li S,Xu D,Xu Y,et al.Security analysis of plastic food packaging[J].Sci Technol Food Ind,2011,32(12):391-393.
[6]谢鸽成.欧洲食品包装材料法规目前的动态[J].塑料助剂,2014,(4):11-13.Xie GC.Development of laws and regulations related food package materials in Europe[J].Plast Addit,2014,(4):11-13.
[7]池海涛,刘颖,高峡,等.食品接触聚丙烯塑料中抗氧化剂迁移模型研究[J].分析化学,2015,43(6):399-403.Chi HT,Liu Y,Gao X,et al.Study on antioxidant migration model in food contact polypropylene plastics[J].Chin J Anal Chem,2015,43(6):399-403.
[8]郝倩,苏荣欣,齐崴,等.食品包装材料中有害物质迁移行为的研究进展[J].食品科学,2014,35(21):279-286.Hao Q,Su RX,Qi W,et al.Review of current knowledge on the migration of harmful substances from food packaging materials[J].Food Sci,2014,35(21):279-286.
[9]薛山,赵国华.食品包装材料中有害物质迁移的研究进展[J].食品工业科技,2012,33(2):404-409.Xue S,Zhao GH.Research progress on migration of harmful substances from food packaging materials[J].Sci Technol Food Ind,2012,33(2):404-409.
[10]Yasar KE,Furkan A.Migration of bis-phenol-a into the natural spring water packaged in polycarbonate carboys[J].Int J Appl Sci Technol,2012,2(1):152-156.
[11]林勤保,李小梅,宋欢,等.聚乙烯塑料包装材料中4种抗氧化剂向脂肪食品模拟物迁移的研究[J].分析科学学报,2010,26(6):631-635.Lin QB,Li XM,Song H,et al.Study on the migration of four kinds of antioxidants to fat food simulants in polyethylene plastic packaging materials[J].J Anal Sci,2010,26(6):631-635.
[12]池海涛.食品包装材料中添加剂迁移规律及模型研究[D].北京:北京理工大学,2015.Chi HT.Study on additive migration rules and models in food packaging materials[D].Beijing:Beijing Institute of Technology,2015.
[13]Galotto MJ,Torres A,Guarda A,et al.Experimental and theoretical study of LDPE versus different concentrations of Irganox 1076 and different thickness[J].Food Res Int,2010,44(2):566-574.
[14]肖少军,张钦发,向红,等.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[J].食品安全质量检测学报,2014,5(6):1746-1750.Xiao SJ,Zhang QF,Xiang H,et al.Study of predicting equilibrium partition coefficient of migrants in food stimulants from plastic by thermodynamic mathematical modeling[J].J Food Saf Qual,2014,5(6):1746-1750.
[15]李敏雯,肖少军,张钦发.Scatchard-Hildebrand热力学模型在预测PE中有害物质迁移分配系数的应用[J].食品工业科技,2016,37(5):121-125.Li MW,Xiao SJ,Zhang QF,et al.Application of predicting migration partition coefficient of harmful migrantsin PE by Scatchard-Hildebrand thermodynamic modeling[J].Sci Technol Food Ind,2016,37(5):121-125.
[16]张艳,张钦发,肖少军,等.影响Scathard-Hildebrand统计热力学理论预测PVC中增塑剂迁移平衡分配系数的因素[J].食品工业科技,2016,37(17):138-141.Zhang Y,Zhang QF,Xiao SJ,et al.Influencing factors of predicting migration partion coefficient ofplasticizers in PVC by Scatchard-Hildebrand thermodynamic model[J].Sci Technol Food Ind,2016,37(17):138-141.
[17]Elmira AT,Frantz F,Stéphane D.Simple method to calculate partition coefficient of migrant in food stimulant/polymer system[J].J Food Eng,2005,77(1):135-139.
[18]李以圭.金属溶剂萃取热力学[M].北京:清华大学出版社,1988.Li YG.Metal solvent extraction thermodynamics[M].Beijing:Tsinghua University Press,1988.