制备液相色谱-离子色谱法测定二缩三乙二醇二硝酸酯(TEGDN)中阴离子杂质
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摘要
为了测定含能增塑剂二缩三乙二醇二硝酸酯(TEGDN)中的阴离子杂质,采用制备液相色谱-离子色谱法对TEGDN中的阴离子进行定性定量分析。考察了制备液相色谱实验中不同流动相比例、进样量、收集时间对TEGDN中杂质阴离子的分离和收集效果的影响以及离子色谱实验中淋洗液体系和淋洗液流速对阴离子分离效果的影响。结果表明,优化后的制备液相色谱条件为:Eclipse XDB-C18色谱柱(250 mm×9.4 mm,5.0μm),流动相V_(甲醇)∶V_水=50∶50,流速1.5 mL·min~(-1),检测波长210 nm,柱温30℃,进样体积0.25 mL;优化后的离子色谱条件为:Metrosep A Supp 5型阴离子分析柱(250 mm×4.0 mm,5.0μm),淋洗液Na_2CO_3(3.2 mmol·L~(-1))/NaHCO_3(1.0 mmol·L~(-1)),流速0.7 mL·min~(-1),抑制型电导检测器,柱温40℃,进样体积20μL。在优化的制备色谱条件下,TEGDN中的杂质阴离子得到有效分离和收集,在离子色谱测定中,各阴离子线性关系良好,相关系数均大于0.999,检出限为0.0025～0.0100μg·mL~(-1),精密度和重复性试验(n=6)的相对标准偏差均小于2.0%,平均加标回收率为95.5%～103.5%。该方法灵敏度高,重现性好,可用于测定TEGDN7中的阴离子杂质。
To determine anionic impurities in energetic plasticizer triethylene glycol dinitrate(TEGDN),the anions in TEGDN were qualitatively and quantitatively analyzed by a preparative liquid chromatography-ion chromatography method. The effect of different mobile phase ratio,injection volume and collection time on the effect of separation and collection of anionic impurities in TEGDN in preparative liquid chromatographic experiments,and the effect of eluent system and eluent flow rate on the separa-tion effect of anions in ion chromatographic experiments were investigated. Results show that the preparative liquid chromato-graphic conditions after optimization are:Eclipse XDB-C18 chromatographic column(250 mm × 9.4 mm,5.0 μm);mobile phase,V_(methanol)∶V_(water)=50∶50;flow rate,1.5 mL·min~(-1);detection wavelength,210 nm;column temperature,30 ℃;injection volume,0.25 mL. The ion chromatographic conditions after optimization are:Metrosep A Supp 5 anion analysis column(250 mm× 4.0 mm,5.0 μm);3.2 mmol·L~(-1) Na_2CO_3/1.0 mmol·L~(-1) NaHCO_3 solution as eluent;flow rate,0.7 mL·min~(-1);sup-pression conductivity detector;column temperature,40 ℃;injection volume,20 μL. Under the optimized preparative liquid chromatographic conditions,anionic impurities in TEGDN are effectively separated and collected. Under the optimized ion chro-matographic conditions,the linearity of the anions is good,the linear correlation coefficients are greater than 0.999;the detec-tion limits of anions are 0.0025-0.0100 μg·mL~(-1). The relative standard deviations of the precision test(n=6)and the repeatabili-ty test(n=6)are less than 2.0%,the average recoveries of anions are 95.5%-103.5%. The method has high sensitivity and good reproducibility,can be used for the determination of the anionic impurities in TEGDN.
To determine anionic impurities in energetic plasticizer triethylene glycol dinitrate(TEGDN),the anions in TEGDN were qualitatively and quantitatively analyzed by a preparative liquid chromatography-ion chromatography method. The effect of different mobile phase ratio,injection volume and collection time on the effect of separation and collection of anionic impurities in TEGDN in preparative liquid chromatographic experiments,and the effect of eluent system and eluent flow rate on the separa-tion effect of anions in ion chromatographic experiments were investigated. Results show that the preparative liquid chromato-graphic conditions after optimization are:Eclipse XDB-C18 chromatographic column(250 mm × 9.4 mm,5.0 μm);mobile phase,V_(methanol)∶V_(water)=50∶50;flow rate,1.5 mL·min~(-1);detection wavelength,210 nm;column temperature,30 ℃;injection volume,0.25 mL. The ion chromatographic conditions after optimization are:Metrosep A Supp 5 anion analysis column(250 mm× 4.0 mm,5.0 μm);3.2 mmol·L~(-1) Na_2CO_3/1.0 mmol·L~(-1) NaHCO_3 solution as eluent;flow rate,0.7 mL·min~(-1);sup-pression conductivity detector;column temperature,40 ℃;injection volume,20 μL. Under the optimized preparative liquid chromatographic conditions,anionic impurities in TEGDN are effectively separated and collected. Under the optimized ion chro-matographic conditions,the linearity of the anions is good,the linear correlation coefficients are greater than 0.999;the detec-tion limits of anions are 0.0025-0.0100 μg·mL~(-1). The relative standard deviations of the precision test(n=6)and the repeatabili-ty test(n=6)are less than 2.0%,the average recoveries of anions are 95.5%-103.5%. The method has high sensitivity and good reproducibility,can be used for the determination of the anionic impurities in TEGDN.
引文
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[12]王少明,荀其宁,许峰.离子色谱分析的样品前处理方法[J].化学分析计量,2005,14(4):59-62.WANG Shao-ming,XUN Qi-ning,XU Feng. Sample pretreat-ment methods for ion chromatographic analysis[J]. Chemical Analysis and Meterage,2005,14(4):59-62.
[13]王永禄,王丽瑶.制备型高效液相色谱法及其在中药研究中的应用[J].中医药通报,2006,5(3):60-63.WANG Yong-lu,WANG Li-yao. Preparative high performance liquid chromatography and its application in research of tradi-tional chinese medicine[J]. Traditional Chinese Medicine Jour-nal,2006,5(3):60-63.
[2] WANG Bin-bin,LIAO Xin,WANG Ze-shan,et al. Prepara-tion and properties of a n RDX-based propellant[J]. Propel-lants,Explosives,Pyrotechnics,2017,42(6):649-658.
[3]姬月萍,李普瑞,汪伟,等.含能增塑剂的研究现状及发展[J].火炸药学报,2005,28(4):47-51.JI Yue-Ping,LI Pu-rui,WANG Wei,et al. A review of recent advances of energetic plasticizers[J]. Chinese Journal of Explo-sives&Propellants,2005,28(4):47-51.
[4] ZHENG Xiao-dong,QIU Shao-jun,FENG Li-min,et al. Syn-thesis and properties of poly-isocyanate energetic curing agent[J]. Polymer Bulletin,2006,56(6):563-569.
[5] XIAO Zheng-gang,YING San-jiu,XU Fu-ming. Response of TEGDN propellants to plasma ignition with the same magni-tude of ignition energy as conventional igniters in an interrupt-ed burning simulator[J]. Propellants,Explosives,Pyrotech-nics,2015,40(4):484-490.
[6]王中合,屈小红,乔晓鹏,等.杂质对混合硝酸酯及其含能粘合剂安定性的影响[J].含能材料,2008,16(1):70-72.WANG Zhong-he,QU Xiao-hong,QIAO Xiao-peng,et al. In-fluence of impurity on stability of blend nitrate ester and ener-getic binder[J]. Chinese Journal of Energetic Materials(Han-neng Cailiao),2008,16(1):70-72.
[7] YI Jian-hua,ZHAO Feng-qi,Hu Rong-zu,et al. Thermal safe-ty study on TEGDN/NG/NC gun propellant[J]. Journal of Ener-getic Materials,2010,28(4):285-298.
[8] YAN Shi,KOU Chen-xia,LI Yan-chun,et al. Catalyst effects of nanometer CuCr2O4on the thermal decomposition of TEGDN propellant[J]. Journal of Energetic Materials,2012,30(2):169-182.
[9] Mirzajani V,Farhadi K,Pourmortazavi S M. Catalytic effect of lead oxide nano-and microparticles on thermal decomposi-tion kinetics of energetic compositions containing TEGDN/NC/DAG[J]. Journal of Thermal Analysis&Calorimetry,2017,131(2):937-948.
[10]薛敏,钟旭,孟子晖,等.离子色谱法检测DNTF中痕量阴阳离子残留[J].含能材料,2012,20(5):650-652.XUE Min,ZHONG Xu,MENG Zi-hui,et al. Determination of ionic residues in 3,4-Dinitrofurazan by ionic chromatography J]. Chinese Journal of Energetic Materials(Hanneng Cailiao),2012,20(5):650-652.
[11]曾秀琳,王凤武,方文彦,等.硝酸酯热分解的机理分析[J].原子与分子物理学报,2009,26(5):962-968.ZENG Xiu-lin,WANG Feng-wu,FANG Wen-yan,et al. A study on pyrolysis mechanism nitrates[J]. Journal of Atomic and Molecular Physics,2009,26(5):962-968.
[12]王少明,荀其宁,许峰.离子色谱分析的样品前处理方法[J].化学分析计量,2005,14(4):59-62.WANG Shao-ming,XUN Qi-ning,XU Feng. Sample pretreat-ment methods for ion chromatographic analysis[J]. Chemical Analysis and Meterage,2005,14(4):59-62.
[13]王永禄,王丽瑶.制备型高效液相色谱法及其在中药研究中的应用[J].中医药通报,2006,5(3):60-63.WANG Yong-lu,WANG Li-yao. Preparative high performance liquid chromatography and its application in research of tradi-tional chinese medicine[J]. Traditional Chinese Medicine Jour-nal,2006,5(3):60-63.