Chen Wei-Cheng, Chen Zih-Yu, Ba Yuxia, Wang Bingyang, Chen Guofei, Fang Xingzhong, Kuo Shiao-Wei
Department of Materials and Optoelectronic Science, College of Semiconductor and Advanced Technology Research, Center for Functional Polymers and Supramolecular Materials, National Sun Yat-Sen University, Kaohsiung 80424, Taiwan.
Dongying Xinbang Electronic Technology Co., Ltd., Dongying 257000, China.
Polymers (Basel). 2022 Jun 12;14(12):2380. doi: 10.3390/polym14122380.
In this study, we synthesized bismaleimide into a functionalized double-decker silsesquioxane (DDSQ) cage. This was achieved by hydrosilylation of DDSQ with nadic anhydride (ND), reacting it with excess -phenylenediamine to obtain DDSQ-ND-NH, and treating with maleic anhydride (MA), which finally created a DDSQ-BMI cage structure. We observed that the thermal decomposition temperature () and char yield were both increased upon increasing the thermal polymerization temperature, and that these two values were both significantly higher than pure BMI without the DDSQ cage structure since the inorganic DDSQ nanoparticle could strongly enhance the thermal stability based on the nano-reinforcement effect. Based on FTIR, TGA, and DMA analyses, it was found that blending epoxy resin with the DDSQ-BMI cage to form epoxy/DDSQ-BMI hybrids could also enhance the thermal and mechanical properties of epoxy resin due to the organic/inorganic network formation created by the ring-opening polymerization of the epoxy group and the addition polymerization of the BMI group due to the combination of the inorganic DDSQ cage structure and hydrogen bonding effect. The epoxy/DDSQ-BMI = 1/1 hybrid system displayed high value (188 °C), value (397 °C), and char yield (40.4 wt%), which was much higher than that of the typical DGEBA type epoxy resin with various organic curing agents.
在本研究中，我们将双马来酰亚胺合成到功能化的双层倍半硅氧烷（DDSQ）笼中。这是通过DDSQ与降冰片烯二酸酐（ND）进行硅氢加成反应，使其与过量的对苯二胺反应得到DDSQ-ND-NH，然后用马来酸酐（MA）处理来实现的，最终形成了DDSQ-BMI笼状结构。我们观察到，随着热聚合温度的升高，热分解温度（）和残炭率均有所增加，并且这两个值均显著高于没有DDSQ笼状结构的纯BMI，因为无机DDSQ纳米颗粒基于纳米增强效应可强烈提高热稳定性。基于傅里叶变换红外光谱（FTIR）、热重分析（TGA）和动态热机械分析（DMA），发现将环氧树脂与DDSQ-BMI笼混合形成环氧/DDSQ-BMI杂化材料，由于无机DDSQ笼状结构与氢键效应的结合，环氧基团的开环聚合和BMI基团的加成聚合形成有机/无机网络，也可提高环氧树脂的热性能和力学性能。环氧/DDSQ-BMI = 1/1的杂化体系显示出高的 值（188℃）、 值（397℃）和残炭率（40.4 wt%），远高于使用各种有机固化剂的典型双酚A型环氧树脂。
