双酚芴双胺型苯并嗯嗪树脂的合成、结构及热性能

摘要

9,9-Bis(4-hydroxyphenyl)-fluorene( bisphenol fluorene, BHPF) was synthesized from phenol and 9-fluorenone using 98％ sulfuric acid as catalyst and 2-mercaptopropionic as promoter, and then a linear BHPF-diamine benzoxazine( BF-eda resin) was synthesized using BHPF, ethylenediamine and paraformaldehyde. The chemical structure of BHPF and BF-eda resin were verified by Fourier transform infrared spectroscopy (FTIR), 1H and 13C nuclear magnetic resonance spectroscopies(NMR). The GPC analysis presents the number average molecular weight of BF-eda resin is 4690, and the polydispersity index ( PDI ) is 2.93. The curing behavior of BF-eda resin was studied by differential scanning calorimetry( DSC ) and the thermal stabilization of polybenzoxazine was evaluated with thermogravimetric analysis(TGA). The ring-opening polymerization temperature of BF-eda resin is about 253 ℃, the thermal decomposition temperature of polybenzoxazine is 344 ℃, the temperature at 5％ weight loss is 357 ℃, and the char yield ratio is 51％ at 900 ℃.%以9-芴酮、苯酚为原料,以质量分数为98%的浓硫酸为催化剂,2-巯基丙酸为助催化剂,合成了双酚芴[9,9-双(4-羟苯基)芴],再用其与乙二胺和多聚甲醛反应,合成了线性双酚芴双胺型苯并噁嗪树脂(BF-eda树脂).采用FTIR,'H NME和<'13>C NMR等分析手段对双酚芴和BF-eda树脂的化学结构进行了表征;用凝胶渗透色谱法测得BF-eda树脂的数均分子量为4690,分子量分布PDI为2.93;采用DSC对BF-eda树脂的热固化行为进行了研究,并使用TGA分析了所得聚苯并噁嗪的热稳定性.在N<,2>气氛中,BF-eda树脂在253℃左右开环聚合,聚苯并噁嗪的分解温度为344℃,失重5%时的温度为357℃,900℃时的残炭率为51%.