超高效液相色谱法测定食品接触材料中5种丙烯酸类化合物的迁移量及其迁移规律探讨

Determination of Migrations of 5 Acrylic Compounds in Food Contact Materials by Ultra-High Performance Liquid Chromatography and Discussion of Their Migration Rules

提出了超高效液相色谱法测定食品接触材料中丙烯酸、丙烯酸甲酯、丙烯酸-2-羟乙基酯、甲基丙烯酸、2-羟乙基-2-甲基-2-丙烯酸酯等5种丙烯酸类化合物迁移量的方法。以水、20%(体积分数,下同)乙醇溶液、4%(体积分数)乙酸溶液、橄榄油作食品模拟物,按照GB 31604.1—2015和GB 5009.156—2016的要求,水基模拟物的浸泡液过0.22μm有机滤膜直接进样分析;取橄榄油浸泡液5 g置于50 mL离心管中,加入5 mL甲醇,涡旋2 min,以转速8 000 r·min^(-1)离心5 min,过0.22μm有机滤膜,滤液上机分析。以Xbridge BEH C_(18)色谱柱为固定相,以不同体积比的0.1%(体积分数)磷酸溶液-乙腈混合液为流动相进行梯度洗脱,在210 nm处用光电二极管阵列检测器测定。结果表明,水基模拟物中丙烯酸类化合物的质量浓度均在0.3~10.0 mg·L^(-1)内与对应的峰面积呈线性关系,检出限(3S/N)均为0.1 mg·L^(-1),橄榄油中丙烯酸类化合物的质量分数均在0.3~10.0 mg·kg^(-1)内与对应的峰面积呈线性关系,检出限(3S/N)均为0.1 mg·kg^(-1);按照标准加入法进行回收试验,回收率为80.6%~99.8%,测定值的相对标准偏差(n=6)均小于8.0%;方法用于食品接触材料样品的分析,其中1份样品中检出丙烯酸甲酯。探究阳性食品接触材料中丙烯酸甲酯在不同模拟物、不同迁移温度和不同迁移时间下的迁移规律,结果表明,丙烯酸类化合物在20%乙醇溶液和橄榄油中迁移能力较强,迁移量随迁移温度的升高而增大,达到最大值后增幅趋于平稳,迁移量达到最大值所需迁移时间也随迁移温度的升高而缩短。

A method for determination of migrations of 5 acrylic compounds in food contact materials,including acrylic acid,methyl acrylate,2-hydroxyethyl acrylate,methacrylic acid,and 2-hydroxyethyl-2-methyl-2-acrylate,was proposed by ultrahigh performance liquid chromatography.Migration tests were conducted using water,20%(volume fraction,the same below)ethanol solution,4%(volume fraction),acetic acid solution,and olive oil as food simulants in accordance with the provisions of GB 31604.1—2015 and GB 5009.156—2016.Direct injection analysis was made on the soaking solution of water-based simulants,which passed through a 0.22 μm organic filter membrane.5 g of olive oil soaking solution was taken,and placed in a 50 mL-centrifuge tube,and 5 mL of methanol was added.The mixed solution was vortexed for 2 min,centrifuged at a rotational speed of 8 000 r · min^(-1) for 5 min,and passed through a 0.22 μm organic filter membrane.The filtrate was analyzed by the instrument.Xbridge BEH C_(18 )chromatographic column was used as the stationary phase and the mixed solution composed of 0.1%(volume fraction) phosphoric acid solution and acetonitrile at different volume ratios was used as mobile phase for gradient elution.The solution was determined at 210 nm by a photodiode array detector.As shown by the results,linear relationships between the corresponding peak areas and mass concentrations of acrylic compounds in the water-based simulants were kept in the range of 0.3-10.0 mg · L^(-1),with detection limits(3S/N) of 0.1 mg · L^(-1).Linear relationships between the corresponding peak areas and mass fractions of acrylic compounds in the olive oil were kept in the range of 0.3-10.0 mg · kg^(-1),with detection limits(3S/N)of 0.1 mg · kg^(-1).Test for recovery was made by the standard addition method,giving results in the range of 80.6%-99.8%,with RSDs(n=6) of the determined values less than 8.0%.This method was used for the analysis of food contact material samples,and methyl acrylate was detected in one of the samples.The migration rules of methyl acrylate in positive food contact materials were investigated under different simulants,different migration temperatures and different migration time.As shown by the results,acrylic compounds had strong migration ability in 20% ethanol solution and olive oil,and the migrations increased with the increase of migration temperature.The growth rate of migration was tended to stabilize after reached the maximum,and the migration time of the maximum migration was shortened with the increase of temperature.