芴基苯并f嗪单体合成及热性能研究.docVIP

芴基苯并f嗪单体合成及热性能研究 　　摘要:本文以双酚芴、环己胺和甲醛为原料,采用混合溶剂法合成了一种新型双官能度芴基苯并?f嗪单体,利用FTIR、1H NMR和13C NMR对产物结构进行了表征,以差式扫描量热仪(DSC)研究了芴基苯并?f嗪单体的固化行为,通过DSC和热重(TGA)分析了聚苯并?f嗪的热性能.结果表明,芴基聚苯并?f嗪树脂呈现出典型的热开环固化特征,放热峰顶温度为251 ordm;C,玻璃化转变温度(Tg)为189.4 ordm;C,初始热分解温度(热失重5%)达329 ordm;C,800 ordm;C时的残碳率达到31%. 　　关键词:双酚芴;苯并?f嗪;合成;热性能 　　中图分类号:TQ 323.1 文献标识码:A 　　Synthesis and thermal properties of a fluorene-containing benzoxazine 　　WANG Jun, WU Ming-qing, LIU Wen-bin, YANG Shi-wei, SHEN Xian-de 　　(College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin, Heilongjiang 150001, China) 　　Abstract: A novel difunctional fluorene-based benzoxazine monomer was synthesized from the reaction of 9,9-bis-(4-hydroxyphenyl)-fluorene with formaldehyde and cyclohexylamine. The chemical structure was confirmed by FTIR, 1H NMR and 13C NMR analyses. The polymerization reaction of the precursor was monitored by differential scanning calorimetry (DSC) and FTIR. The thermal properties of cured polymers were evaluated with DSC and thermogravimetric analysis (TGA). The fluorene-based polybenzoxazine shows the typical curing characteristic of oxazine ring-opening for difunctional benzoxazine centred at 251 ordm;C, and remarkably higher glass transition temperature (189.4 ordm;C) and better thermal stability than traditional biphenol A polybenzoxazines. The thermal decomposition temperature (5% weight loss) and char yield at 800 ordm;C of fluorene based polybenzoxazine is 329 ordm;C and 31%, respectively. 　　Key Words: bisphenol flourene; benzoxazine;synthesis; thermal properties 　　 　　聚苯并?f嗪是在传统酚醛树脂的基础上发展起来的一种新型热固性树脂.此类树脂除具有酚醛树脂优良的耐热性和阻燃性外,还在一定程度上改善了酚醛树脂的脆性和尺寸不稳定性,最显著的优点是通过自身开环聚合形成三维网络结构,固化时无小分子释放,制品孔隙率低,其体积近似零收缩,有高的Tg和热稳定性,以及良好的机械性能、电气性能、阻燃性能和高的残碳率[1-2],因而在先进复合材料基体树脂、耐烧蚀树脂、电子产品密封材料等方面应用较广[3-4].苯并?f嗪单体通常是由单酚或双酚与甲醛和伯胺在氯仿、二氧六环等非极性溶剂或无溶剂存在下经缩合反应生成.其中,双酚型苯并?f嗪主要有双酚A、萘二酚、联苯二酚、二羟基二苯甲酮等主链型结构,大量的双酚和伯胺使得苯并?f嗪具有灵活的分子设计性.而通过在酚类或胺类分子中引入烯基、炔基、腈基、马来酰亚胺基、环氧基等功能性基团,或与环氧、聚酰亚胺、聚氨酯等树脂进行共混改性,可得到性能各异的功能性