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
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摘要
为更加准确预测PE塑料中化合物向食品中迁移的分配系数。以PE中抗氧剂为代表,从大量文献中筛选PE中有害迁移物向食品模拟液迁移测试的可靠实验数据,将分配系数实验值F_(exp)与模型预测分配系数计算值F_(sim)对比分析,并对Scatchard-Hildebrand热力学模型进行实验校正,研究了温度(T)、迁移物分子量(M)和醇-水分配系数(log P)以及模拟液极性(ln Ps)与修正系数Ks(Ks=ln(F_(sim)/F_(exp))的关系。结果表明除个别化合物因其分子结构特殊外,PE中化学物向脂肪类食品模拟液中迁移分配系数预测模型的修正系数Ks与M、log P、ln Ps均呈显著的线性相关性,得到修正后的Scatchard-Hildebrand热力学模型F'_(sim)=exp(V迁移物/RT·[φ_(模拟液)~2(δ_(迁移物)-δ_(模拟液))~2-φ_(聚合物)~2(δ_(迁移物)-δ_(聚合物))~2]-7.289-0.021M-1.317ln Ps+0.901log P),其在一定程度上能够预测PE中有害物质向脂肪类食品模拟物中迁移的分配系数。
The objective of this study was to predict the partition coefficient of compounds in PE plastic migrant to food more accurately. A large number of literatures and the experimental test data of harmful chemicals in PE migrant to different food simulations were collected. Then the experimental partition coefficient value F_(exp) and the predicted one F_(sim) were contrasted and analyzed. And the Scatchard- Hildebrand thermodynamic model was corrected with experimental value. The correlations between the correction coefficient Ks( Ks = ln( F_(sim)/ F_(exp))) and temperature( T),migration molecular weight( M),migration alcohol / water partition coefficient( log P) and simulation liquid polarity( ln Ps) were investigated. Results showed that,in addition to the individual compound with special molecular structure,significant linear correlations were found between the correction coefficient Ks of partition coefficient predictive model of chemicals in PE migrant to fat food simulations and M,log P and ln Ps. Finally,the corrected Scatchard- Hildebrand thermodynamic model F'_(sim)= exp( V_(迁移物)/ RT·[φ_(模拟液)~2(δ_(迁移物)-δ_(模拟液))~2-φ_(聚合物)~2(δ_(迁移物)-δ_(聚合物))~2]-7.289-0.021M-1.317 ln Ps + 0.901 log P) was set up.To some extent,it could predict partition coefficient of compounds in PE plastic migrant to fat food simulations.
The objective of this study was to predict the partition coefficient of compounds in PE plastic migrant to food more accurately. A large number of literatures and the experimental test data of harmful chemicals in PE migrant to different food simulations were collected. Then the experimental partition coefficient value F_(exp) and the predicted one F_(sim) were contrasted and analyzed. And the Scatchard- Hildebrand thermodynamic model was corrected with experimental value. The correlations between the correction coefficient Ks( Ks = ln( F_(sim)/ F_(exp))) and temperature( T),migration molecular weight( M),migration alcohol / water partition coefficient( log P) and simulation liquid polarity( ln Ps) were investigated. Results showed that,in addition to the individual compound with special molecular structure,significant linear correlations were found between the correction coefficient Ks of partition coefficient predictive model of chemicals in PE migrant to fat food simulations and M,log P and ln Ps. Finally,the corrected Scatchard- Hildebrand thermodynamic model F'_(sim)= exp( V_(迁移物)/ RT·[φ_(模拟液)~2(δ_(迁移物)-δ_(模拟液))~2-φ_(聚合物)~2(δ_(迁移物)-δ_(聚合物))~2]-7.289-0.021M-1.317 ln Ps + 0.901 log P) was set up.To some extent,it could predict partition coefficient of compounds in PE plastic migrant to fat food simulations.
引文
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[2]皮林格,巴纳主编.范家起,张玉霞译.食品用塑料包装材料——阻隔功能、传质、品质保证和立法[M].北京:化学工业出版社,2004.
[3]李以圭.金属溶剂萃取热力学[M].北京:清华大学出版社,1988:145-152.
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[6]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.
[7]项文娟,郭小然,韩静.溶解度参数在固体分散体中的应用[J].今日药学,2010,20(12):5-8.
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[11]林勤保,李小梅,宋欢,等.聚乙烯塑料包装材料中4中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.
[12]李小梅.塑料与纸质食品包装材料中抗氧化剂的测定及迁移研究[D].大同:山西大学,2010.
[13]胡长鹰,黄肖红.HDPE膜中抗氧剂1076向替代脂肪类食品模拟物迁移的研究[J].食品工业科技,2009,30(2):244-247.
[14]黄肖红.HDPE膜中抗氧化剂1076向食品或食品模拟物的迁移研究[D].广州:暨南大学,2008.
[15]赵威威.塑料包装材料中化学物向脂肪类食品的迁移研究[D].无锡:江南大学,2007.
[16]http://getdata-graph-digitizer.com/registration.php
[17]Ozaki A,Gruner A,Stoermer A,et al.Correlation between partition coefficients polymer/food simulant,KP,Fand octanol/water Log POW-a new approach in support of migration modeling and compliance testing[J].Deutsche Lebensmittel-Rundschau,2010,106(4):203-208.
[18]邸晓贺.星型抗氧剂的设计合成与性能研究[D].大庆:大庆石油学院,2007:18-20.
[19]黄秀玲,王志伟,李明.影响PE淋膜纸中化学迁移物分配系数的因素[J].高分子材料科学与工程,2010,26(8):23-26.
[2]皮林格,巴纳主编.范家起,张玉霞译.食品用塑料包装材料——阻隔功能、传质、品质保证和立法[M].北京:化学工业出版社,2004.
[3]李以圭.金属溶剂萃取热力学[M].北京:清华大学出版社,1988:145-152.
[4]Gillet G,Vitrac O,Desobry S.Prediction of partition coefficients of plastic additives between packaging materials and food simulants[J].Industrial&Engineering Chemistry Research,2010,49(16):7263-7280.
[5]Piringer OG,Baner AL.Plastic packaging:interactions with food and pharmaceuticals[M].Second,Completely Revised Edition.Weinheim:Wiley-VCH,2008.504.
[6]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.
[7]项文娟,郭小然,韩静.溶解度参数在固体分散体中的应用[J].今日药学,2010,20(12):5-8.
[8]Hansen CM.Hansen solubility parameters-A User’s Handbook[M].New York:CRC Press,2000.
[9]Tehrany E A,Brandsch J,Mercea P,et al.Simple method to calculate partition coefficient of migrant in food simulant/polymer system[J].Journal of Food Engineering,2006,77:135-139.
[10]李挥,墨伟,范斌,等.食品包装材料迁移实验方法和食品模拟物选择[J].塑料助剂,2008,2:13-17.
[11]林勤保,李小梅,宋欢,等.聚乙烯塑料包装材料中4中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.
[12]李小梅.塑料与纸质食品包装材料中抗氧化剂的测定及迁移研究[D].大同:山西大学,2010.
[13]胡长鹰,黄肖红.HDPE膜中抗氧剂1076向替代脂肪类食品模拟物迁移的研究[J].食品工业科技,2009,30(2):244-247.
[14]黄肖红.HDPE膜中抗氧化剂1076向食品或食品模拟物的迁移研究[D].广州:暨南大学,2008.
[15]赵威威.塑料包装材料中化学物向脂肪类食品的迁移研究[D].无锡:江南大学,2007.
[16]http://getdata-graph-digitizer.com/registration.php
[17]Ozaki A,Gruner A,Stoermer A,et al.Correlation between partition coefficients polymer/food simulant,KP,Fand octanol/water Log POW-a new approach in support of migration modeling and compliance testing[J].Deutsche Lebensmittel-Rundschau,2010,106(4):203-208.
[18]邸晓贺.星型抗氧剂的设计合成与性能研究[D].大庆:大庆石油学院,2007:18-20.
[19]黄秀玲,王志伟,李明.影响PE淋膜纸中化学迁移物分配系数的因素[J].高分子材料科学与工程,2010,26(8):23-26.