【作者】 张涛；

【导师】 袁荞龙；

【作者基本信息】 华东理工大学 ， 材料科学与工程， 2014， 硕士

【摘要】 以提高苯并嗯嗪树脂的性能为目的,借助苯并嗯嗪分子结构设计的灵活性,通过在酚源以及胺源中引入官能团以及改变官能团的空间位置,合成了一系列含有官能团的苯并噁嗪,通过氢谱核磁共振(1HNMR).红外(FTIR)以及元素分析(EA)等进行了表征。利用红外跟踪的方法追踪了苯并噁嗪固化过程中官能团的变化,并依据朗伯-比尔定律进行了官能团转化率的计算。同时,在不同升温速率下用差示扫描量热法(DSC),依据Kissinger和0zawa经验公式计算了各种苯并噁嗪的反应活化能。利用不同温度下的反应凝胶时间的测定和阿伦尼乌斯方程,通过线性拟合对凝胶活化能进行了计算。结果表明,成功合成出含不同官能团的苯并噁嗪,不同方法计算所得到的同种树脂的反应活化能较为接近。通过低场核磁也对苯并嗯嗪树脂的固化过程进行了研究。含有不同官能团的苯并嗯嗪热固化后,对不同苯并噁嗪树脂进行氮气中的热失重分析(TGA)。结果表明,以对氨基苯基炔丙基醚(P-p一appe)、苯酚和多聚甲醛为原料制备的苯并嗯嗪树脂失重5%时的温度最高,为395℃。将酚源为对甲氧基苯酚所合成的含甲氧基的苯并嗯嗪树脂在800℃下的残炭率最高,为64%。对制备的含官能团苯并嗯嗪利用Materials Studio软件进行分子模拟,结果显示,分子的静电能对于分子的热性能存在一定的影响,酚源上不同电子效应的取代基团影响苯并嗯嗪分子的静电能。选用制备的含氰基苯并噁嗪树脂CP-p-appe对含硅芳炔树脂(PSA)进行了改性研究,并制备了T700碳纤维增强改性PSA树脂复合材料。结果显示,在含硅芳炔树脂中混入CP-p-appe以后,复合材料的弯曲性能以及层间剪切强度都有了提升。更多还原

【Abstract】 In order to improve the properties of polybenzoxazines, flexibility of molecular design, one of features of benzoxazine was introduced to design and synthesize benzoxazines with different functional groups. Phenols and amines attached different groups at different position were used as raw materials to produce a series of benzoxazines in this paper. Proton nuclear magnetic resonance (’H NMR), Fourier transform infrared (FTIR) and Elemental Analysis (EA) were used to characterize the benzoxazines with functional groups. The variation of the functional groups in the benzoxazmes during curing was monitored in situ by FTIR. The conversions of the functional groups were calculated according to the Lambert-Bill law. Meanwhile, the benzoxazines were performed on differential scanning calorimeter (DSC) under different heating rate. The apparent activation energies of the benzoxazines during curing were calculated in terms of the empirical Kissinger and Ozawa equations. The gel time of the benzoxazines at different temperature were obtained to be linearly fitted to get the activation energy of gelling in accordance with Arrhenius equation. The results show that the benzoxazines with functional groups were synthesized successfully. The curing activation energy of every benzoxazine calculated by different methods is close to each other. The cure reactions of the benzoxazines were also studied in low-field pulsed nuclear magnetic resonance.The thennal stability of the cured benzoxazines with functional groups was tested in nitrogen by thermogravimetric analysis (TGA). The results show that the temperature at5%mass loss of the cured benzoxazine produced by p-aminophenyl propargyl ether, phenol and paraformaldehyde is the highest value among the cured benzoxazines, it is395℃. The char yield at800℃of the cured benzoxazine produced by p-aminophenyl propargyl ether, p-methoxyl phenol and paraformaldehyde is the highest value, it is64%. The benzoxazines with functional groups were stimulated and modeled by Materials Studio. The results denote that the thennal properties of the cured benzoxazines are influenced by molecular electrostatic energy. The electronic effect of the substituent affects the molecular electrostatic energy. The benzoxazine with propargyl and cyano groups was used to blend with the silicon-containing polyarylacetylene (PSA). Furthennore, the unidirectional carbon fiber (T700CF) was used to reinforce the modified PSA (M-PSA). The flexural property and interlaminar shear strength (ILSS) of the T700CF reinforced M-PSA composites increase.更多还原