抗氧剂168的质量控制分析及杂质鉴定  

Quality Control Method for Tris(2,4-di-tert-butylphenyl) phosphite Production and Identification of Its Impurities

作　　者：李丹妮[1] 刘雯雯[1] 练鸿振[1] 朱劲松[2] 

机构地区：[1]教育部生命分析化学重点实验室南京大学现代分析中心,南京大学化学系南京210093 [2]南京扬子石化精细化工有限责任公司

出　　处：《应用化学》2005年第5期511-516,共6页Chinese Journal of Applied Chemistry

基　　金：南京大学分析测试基金资助项目(04CA5)

摘　　要：建立了测定抗氧剂168及其中有害杂质2,4-二叔丁基苯酚含量的高效液相色谱紫外检测分析方法,确定了0～5min,V(甲醇)∶V(水)为95∶5～100∶0,5～25min,V(甲醇)∶V(水)=100∶0的流动相条件进行梯度洗脱的方法,色谱柱为KromasilC18,5μm,150mm×4.6mm(i.d.),流动相流速为1.0mL/min,柱温为30℃,检测波长为275nm。抗氧剂168与2,4-二叔丁基苯酚的质量浓度分别为1.0×10-6～1.0×10-3g/mL和1.0×10-7～1.0×10-4g/mL时与峰面积呈良好的线性关系,相关系数r分别为0.99994和0.99995,检出限分别为1.0×10-7g/mL和1.0×10-8g/mL,实际样品中抗氧剂168和2,4-二叔丁基苯酚测定的相对标准偏差分别为0.1%和1.8%;并将2,4二叔丁基苯酚的测定结果与分光光度法的测定结果进行了比较。结果显示,分光光度法并不能用于测定抗氧剂168中的2,4二叔丁基苯酚;利用液相色谱质谱联用方法、紫外可见光谱和色谱保留规律,分别定性鉴定了抗氧剂168工业产品中3种脱叔丁基杂质;在0～20min,V(甲醇)∶V(水)=100∶0等度洗脱的流动相条件下,本方法还可应用于复合抗氧剂中抗氧剂168的测定,测定的相对标准偏差为0.7%,回收率为101%。This paper presents a high-performance liquid chromatography-UV detection analytical method for the determination of tris(2,4-di-tert-butylphenyl)phosphite(TBP) and its poisonous impurity (2,4-di-)tert-(butylphenol)(DBP). The separation between TBP and DBP was performed on a Kromasil C_(18) column, 5 μm, 150 mm×4.6 mm(i.d.), and the quantitation was achieved with UV detection at 275 nm. The (column) temperature was maintained at 30 ℃. The mobile phase was a mixture of methanol and water and run at a flow rate of 1.0 mL/min, and a two-step linear gradient elution, 0～5 min, V(methanol)∶V(water)=(95∶5); 5～25 min, V(methanol)∶V(water)=100∶0, was adopted. The calibration curves were (linear) in the concentration ranges of 1.0×10^(-6)～1.0×10^(-3) g/mL of TBP and 1.0×10^(-7)～1.0×10^(-4) g/mL of DBP, respec-(tively), with correlation coefficients of 0.999 94 and 0.999 95. The detection limits were 1.0×10^(-7) g/mL for TBP and 1.0×10^(-8) g/mL for DBP. Good reproducibility was obtained for the determinations of TBP and DBP in real industrial samples with relative standard deviations of 0.1% and 1.8%, respectively. The DBP (analysis) result obtained by HPLC were compared with that by spectrophotometry, and it was found that the (spectrometric) method was (unable) to determine DBP in TBP accurately. Two impurities were identified by (LC-MS). The structure of another impurity was estimated according to its UV-Vis spectrum and chromatographic behavior. All these three impurities in antioxidant 168 were TBP derivatives with fewer tert-butyl substituents. When an isocratic elution was used:((0～)20 min, (V(methanol)∶)V(water)=100∶0), this method was applied to analyze TBP in composite antioxidants with a relative standard deviation of 0.7% and a recovery rate of 101%.

关 键 词：抗氧剂168 二叔丁基苯酚 液相色谱-质谱联用 高效液相色谱 紫外-可见光谱 

分 类 号：O657[理学—分析化学]