色谱

色谱 ›› 2017, Vol. 35 ›› Issue (9): 1008-1013.DOI: 10.3724/SP.J.1123.2017.05015

• 研究论文 • 上一篇    下一篇

气相色谱法测定及预测有机磷阻燃剂的蒸气压

王庆芝, 赵洪霞, 王琰, 谢晴, 陈景文, 全燮   

  1. 工业生态与环境工程教育部重点实验室, 大连理工大学环境学院, 辽宁 大连 116023
  • 收稿日期:2017-05-18 出版日期:2017-09-08 发布日期:2017-09-15
  • 通讯作者: 赵洪霞,E-mail:hxzhao@dlut.edu.cn.
  • 基金资助:

    国家自然科学基金（21677023）；城市水资源与水环境国家重点实验室开放基金项目（QAK201606）.

Determination and prediction for vapor pressures of organophosphate flame retardants by gas chromatography

WANG Qingzhi, ZHAO Hongxia, WANG Yan, XIE Qing, CHEN Jingwen, QUAN Xie   

  1. Key Laboratory of Industrial Ecology and Environmental Engineering of Ministry of Education, School of Environmental Science and Technology, Dalian University of Technology, Dalian 116023, China
  • Received:2017-05-18 Online:2017-09-08 Published:2017-09-15
  • Supported by:

    National Natural Science Foundation of China (No. 21677023); State Key Laboratory Open Foundation of Urban Water Resource and Environment (No. QAK201606).

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摘要：

以p，p'-二氯二苯三氯乙烷（p，p'-DDT）为参考化合物，采用气相色谱法（GC）测定了14种有机磷阻燃剂（OPFRs）在不同温度（T）条件下的蒸气压（PGC）及其蒸发热。根据获得的蒸气压值，发现14种OPFRs的log PGC随着温度的增加而减小。初步探讨了分子结构与log PGC的相关性，结果发现卤代烷基磷酸酯的log PGC低于烷基和芳基磷酸酯，且随着分子摩尔体积的增大，相应的log PGC呈下降趋势。采用逐步回归的方法，建立了OPFRs的相对保留时间（RRT）与log PGC之间的定量构效关系（QSPR）模型，模型的累计交叉有效判别系数Qcum2为0.946。模型对OPFRs的log PGC预测值与实验值有良好的相关性（r=0.980），结果表明所建模型具有良好的稳健性和预测能力。利用建立的方法，通过测定的保留时间参数以及定量构效关系模型，可有效预测目前没有标准品的OPFRs的log PGC值。

关键词: 定量构效关系, 气相色谱, 有机磷阻燃剂, 蒸气压

Abstract:

Organophosphate flame retardants (OPFRs) are ubiquitous in the environment. To better understand and predict their environmental transport and fate, well-defined physicochemical properties are required. Vapor pressures (P) of 14 OPFRs were estimated as a function of temperature (T) by gas chromatography (GC), while 1,1,1-trichioro-2,2-bis (4-chlorophenyl) ethane (p,p'-DDT) was acted as a reference substance. Their log PGC values and internal energies of phase transfer (△ vapH) ranged from -6.17 to -1.25 and 74.1 kJ/mol to 122 kJ/mol, respectively. Substitution pattern and molar volume (VM) were found to be capable of influencing log PGC values of the OPFRs. The halogenated alkyl-OPFRs had lower log PGC values than aryl-or alkyl-OPFRs. The bigger the molar volume was, the smaller the log PGC value was. In addition, a quantitative structure-property relationship (QSPR) model of log PGC versus different relative retention times (RRTs) was developed with a high cross-validated value (Q2cum) of 0.946, indicating a good predictive ability and stability. Therefore, the log PGC values of the OPFRs without standard substance can be predicted by using their RRTs on different GC columns.

Key words: gas chromatography (GC), organophosphate flame retardants (OPFRs), quantitative structure-property relationship (QSPR), vapor pressure (P)

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