含磷螺环原碳酸酯的制备与性能

Preparation and Properties of a Phosphorous Containing Spiro Orthocarbonate

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和2,2-二羟甲基丁醛(DMB)为原料,合成了DOPO基三元醇(DTHA),再与原碳酸四乙酯(TEOC)发生酯交换反应合成出一种含磷螺环原碳酸酯(SOC)。利用红外光谱、核磁分析和元素分析对合成产物的结构进行了表征。将SOC在三氟化硼乙胺络合物的催化作用下进行阳离子开环聚合,用膨胀计法跟踪测定其膨胀率,对其开环聚合机理进行探讨,并对SOC开环聚合产物的本征阻燃性能进行研究。结果表明,该螺环化合物在160℃进行开环聚合时,体积膨胀率可达5.21%;其开环聚合产物的极限氧指数(LOI)在30%以上,并可通过UL-94 V-0级试验。

A DOPO-based trihydroxy alcohol （DTHA） was synthesized through the reaction of 9,10-dihydro-9- oxa-10-phosphaphenanthrene-10-oxide （DOPO） and 2,2-dimethylol-l-butanal （DMB）, and the spiro orthocarbonate （S O C） was synthesized by transesterification reaction between DTHA and tetraethyl orthocarbonate （TEOC）. The structure of SOC was confirmed by FT-IR, 1H-NMR spectra and elemental analysis. The expansion ratio of SOC was determined by dilatometer. The mechanism of ring-opening polymerization was discussed. The flame retardancy of SOC ring-opening products was also measured. The results show that the volume expansion ratio of SOC is 5.21%, when its ring-opening polymerization occurs at 160 ℃. The LOI of the ring-opening polymerization products is higher than 30 %, and the ring-opening products can reach V-0 classification in UL-94 test.