含氟磷酰胺类化合物的合成及其性能

Synthesis of Fluorinated Phosphoramides and Their Properties

以螺环二磷酰氯1与烯丙胺为原料制备了二烯丙基磷酰胺2.在偶氮二异丁腈(AIBN)引发下,二烯丙基磷酰胺2与全氟己基碘反应得到含双氟烷基链的化合物3和含单氟烷基链的化合物4,并通过三丁基锡氢还原分别得到了含有全氟己基的磷酰胺TM1和TM2,其结构通过核磁共振谱(1 H NMR、13C NMR、19F NMR、31P NMR)、傅里叶变换红外光谱(FTIR)、高分辨质谱(HRMS)等分析进行了表征和确认.对磷酰胺TM1和TM2在棉织物表面的性能研究显示,含双氟烷基链的化合物TM1具有较好的拒油性能,对三级油的接触角最高可达136°,但此化合物没有显示出明显的拒水性能;而含单氟烷基链的化合物TM2则显示出一定的拒水性能,对水的接触角最高可达147°,对三级油的接触角也达到了134°.同时,这两个化合物都具有一定阻燃性能,均使得整理后棉织物的极限氧指数(LOI)值从18.5%提高到了24.0%.

Diallyl phosphoramide 2 was prepared from spirocyclic diphosphoryl chloride 1 with allylamine.Compounds 3 containing double fluoroalkyl chains and 4 containing single fluoroalkyl chain were obtained from diallyl phosphoramide 2 and tridecafluorohexyl iodide using azobisisobutyrinitrile（AIBN）as an initiator.Then phosphamides TM1 and TM2 containing perfluorohexyl were gained through the reduction of compounds 3 and 4 with tributyltin hydride,respectively.The structures of these compounds have been characterized by nuclear magnetic resonance（1 H NMR、13 C NMR、19 F NMR、31P NMR）、Fourier transform infrared spectroscopy（FTIR）and high resolution mass spectrometry（HRMS）.The studies of the properties of phosphoramides TM1 and TM2 on the surface of cotton fabric show that TM1 containing double fluoroalkyl chains have good oil-repellent properties and the contact angles of Grade 3 oil reach136°while it has no water repellency performance.However,TM2 containing single fluoroalkyl chain has good water and oil-repellent property and the contact angles of water and Grade 3 oil reach up to 147°and 134°respectively.These two compounds show certain flame retardant property as the limited oxygen index（LOI）value of cotton fabrics improves from18.5%to 24.0%.