三(1-氧代-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷-4-亚甲基)磷酸酯的合成、晶体结构及热性能

由季戊四醇和三氯氧磷出发，经由两步反应合成了三（1－氧代－1－磷杂－2，6－7－三氧杂双环2.2.2]辛烷－4－亚甲基）磷酸酯（Trimer)，并采用元素分析，FTIR，^1H NMR,^31P NMR及X射线四圆 新化合物的分子结构。结果分析表明，Trimer分子中含3个结构高度对称的双环笼状磷酸酯单元，属单斜晶系，Cc空间群，晶胞系数为a=1.2754(3)nm,b=1.8582(4)nm,c=1.1269(2)nm,V=2.3242(8)nm^3,Z=4，最终偏离因子R＝0.0322,Rω＝0．0907。TG－DTA与DSC结果表明，Trimer具有优异的热稳定性与成炭性能，将成为一种高效能的膨胀型阻燃剂。

Synthesis, Structure and Thermal Property of Tri(1-oxo-2,6,7-trioxa-l-phosphabicyclo[2.2.2]octane-methyl)phosphate

A novel caged bicyclic phosphate flame retardant tri(1-oxo-2, 6, 7-trioxa-1-phosphabicyclo2.2.2]octane-methyl) phosphate (Trimer) was synthesized from 1-oxo-4-hydroxymethyl-2, 6, 7-trioxal-phos-phabicyclo2. 2. 2]octane(PEPA) and phosphorus oxychloride in this paper. Its structure was character-ized by elemental analysis, FTIR, 1H NMR, 31P NMR and X-ray diffraction analysis. The crystals aremonoclinic, space group Cc, with unit cell dimensions a= 1. 275 4(3) nm, b=1. 858 2(4) nm, c=1.1269(2)nm, V= 2.324 2(8) nm3, four molecules per unit cell. The final R=0.032 2, Rw=0.090 7 for 2177 unique reflections. The crystal data reveal that the three cages in Trimer are structurally equivalent,and that the corresponding average bond lengths and bond angles are appropriate. The results of TG-DTAand DSC have convincingly demonstrated that Trimer has an excellent thermal stability and char formingcharacteristics, which is expected to be a promising intumescent flame retardant.