1,2,3-三(5,5-二甲基-1,3-二氧杂环己内磷酰氧基)苯的合成、 晶体结构及阻燃性能研究

以新戊二醇、三氯氧磷以及1,2,3-三羟基苯等为原料, 经过两步反应合成新型阻燃剂1,2,3-三(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯, 采用元素分析、FTIR、MS、1H NMR及X射线四圆衍射等技术确定了标题化合物的分子结构. 结构分析表明, 该标题化合物属于三斜晶系, P-1空间群, 每个结构单元含有2个分子, 晶胞参数为a＝0.70450(14) nm, b＝1.2850(3) nm, c＝1.5609(3) nm, α＝69.19(3)°, β＝86.29(3)°, γ＝86.60(3)°, V＝1.3171(5) nm3, Dc＝1.438 g/cm3, μ＝0.286 mm－1, F(000)＝600, Z＝2, 由4635个独立衍射点得到最终偏离因子[I＞2σ(I)] R＝0.0574, Rw＝0.1061. 实验分析表明, 该标题化合物具有良好的热稳定性和成炭性, 对环氧树脂具有较好的阻燃效果, 最佳添加量为20%.

Synthesis, Structure and Flame Retardant Property of 1,2,3-Tris(5,5-dimethyl-1,3-dioxaphosphorinanyl-2-oxy)benzene

The novel flame retardant 1,2,3-tris(5,5-dimethyl-1,3-dioxaphosphorinanyl-2-oxy)benzene was synthesized via neopentyl alcohol, phosphous oxychloride, 1,2,3-trihydroxybenzene by a two step reaction, and its structure identified and studied by elemental analysis, IR, 1H NMR, MS techniques and X-ray diffraction analysis. The crystal belongs to triclinic, space group P-1 with unit cell dimensions a＝0.70450(14) nm, b＝1.2850(3) nm, c＝1.5609(3) nm, α＝69.19(3)°, β＝86.29(3)°, γ＝86.60(3)°, V＝1.3171(5) nm3, Dc＝1.438 g/cm3, μ＝0.286 mm－1, F(000)＝600 and Z＝2. The final R＝0.0574 and Rw＝0.1061 for 4635 unique reflections [I＞2σ(I)]. The result of thermal analysis shows that the novel flame retardant has a high thermal stability and excellent char forming ability. The results demonstrate that the title compound is effective on the flame retardancy of epoxy resin, and the optimum addition content is 20%.