有机磷阻燃剂气相色谱-四极杆飞行时间质谱裂解机理研究  

Fragmentation Mechanism of Organic Phosphorus Flame Retardant by Gas Chromatography-Quadrupole Time of Flight Mass Spectrometry

作　　者：杨吉双 张庆合[2] 苏立强[1] YANG Ji-shuang;ZHANG Qing-he;SU Li-qiang(College of Chemistry and Chemical Engineering,Qiqihar University,Qiqihar 161006,China;Division of Chemical Metrology and Analytical Science,National Institute of Metrology,Beijing 100029,China)

机构地区：[1]齐齐哈尔大学化学与化学工程学院,黑龙江齐齐哈尔161006 [2]中国计量科学研究院化学计量与分析科学研究所,北京100029

出　　处：《质谱学报》2021年第1期36-47,I0002,共13页Journal of Chinese Mass Spectrometry Society

基　　金：公益性科研院所基本科研业务费(AKYZD1906)资助。

摘　　要：利用气相色谱-四极杆飞行时间质谱法(GC-QTOF MS),在全扫描模式下,采用电子轰击离子源(EI)对烷基类、氯化类和芳香类等17种有机磷阻燃剂(OPFRs)的质谱裂解机理进行探究。结果表明,在50 eV电离能下,各化合物碎片离子丰度较高且相对稳定。烷基类和氯化类OPFRs通常会发生3次γ-H重排,C—O键断裂后分别形成[M-R+2H]^+、[M-2R+3H]^+、[M-3R+4H]^+碎片离子,支链氯化类OPFRs易失去—CH2Cl;芳香类OPFRs更易断裂P—O键得到相应碎片;同时发现,邻、间、对磷酸三甲苯酯碎片离子种类基本相似,但碎片丰度却存在明显差异。这3类OPFRs在碎裂过程中均伴随失水现象。本研究通过探究OPFRs各化合物质谱裂解机理,建立了全扫描模式下OPFRs精确质量数据库,为此类化合物的结构鉴定提供了依据。With the restriction of the use for bromine flame retardants,organophosphorus flame retardants(OPFRs)have been used as excellent substitutes.However,owing to OPFRs are not chemically bound to the materials,they can be easily released from materials to the environment and be exposed to humans by inhalation,ingestion,and dermal adsorption.Furthermore,OPFRs can cause neurotoxicity,carcinogenicity and reproductive toxicity.According to different types of substituents,OPFRs are mainly divided into alkyls,halogenated and aromatics,which have a great variation in physicochemical properties.Depending on the superiority of high resolution,fast acquisition rates,precise mass full-spectrum acquisition of time-of-flight mass spectrometry,it has been widely used to analyze fragmentation mechanism of complex compound.In this paper,the fragmentation mechanism of 17 OPFRs was investigated by using gas chromatography-quadrupole time-of-flight mass spectrometry(GC-QTOF MS)technology at full-scan mode with EI ionization.The experimental results indicated that the ion fragment of these compounds is relatively high and stable at 50 eV of ionization energy.In general,under EI ion source,the alkyls and halogenated OPFRs undergo threeγ-H rearrangements,and provide[M-R+2 H]+,[M-2 R+3 H]+and[M-3 R+4 H]+ion fragments.The chlorinated OPFRs are prone to lose[CH2Cl]+and Cl-groups due to specific chemical structures.The aromatic OPFRs are relatively stable due to the conjugation effect,so the molecular ion is the most abundant ion.In addition,the P—O bond is more easily broken to obtain phenol radical ion fragments with higher abundance.For example,o-,m-,and p-trimethyl phosphate are likely to break up P—O bond,but the abundance of fragments are significantly different.Finally,the three types of compounds are often accompanied by water loss during the fragmentation process and rearrangement.By comparing the ion abundance ratio of each compound fragment,the[H4PO4]+(m/z 99)would be optimal for the quantitation of alkyls and halogenated OPFR

关 键 词：有机磷阻燃剂 气相色谱-四极杆飞行时间质谱(GC-QTOF MS) 裂解机理 

分 类 号：O657.63[理学—分析化学]