Rigid Polymer Network with Nano pores and its Application for High Performance Materials

以2,5 -二氨基- 1,4 -苯二硫醇为原料，用对苯二甲酸（TPA）和三羧酸（TMA）的混合物缩聚制备了刚性聚合物网络。表观密度与TPA/TMA比值有关，远小于线性PBZT (1.57 g/cm^3)，表明网络内存在许多纳米空隙。由于该部分非常坚硬，许多COOH在空隙周围留下。ε-己内酰胺使网络膨胀两倍，聚合成尼龙浸渍刚性聚合物网络的复合形式。用甲酸从复合材料中提取游离尼龙6，结果表明，四分之一的尼龙6直接接枝到刚性聚合物网络上。DSC测量表明接枝尼龙6不能结晶。另一方面，通过在凝胶化之前停止缩聚，制备了直径为几百nm的PBZT网络颗粒。用ε-己内酰胺膨胀法制备复合膜。PBZT网与尼龙6的比例为1/3，复合膜的表观密度为1.23 g/cm^3，高于纯尼龙6膜的1.16 g/cm^3。该复合材料的力学性能得到了显著改善。

Rigid polymer networks were prepared by polycondensation of 2, 5-diamino-1, 4-benzene-dithiol with a mixture of terephthalic acid (TPA) and trimesic acid (TMA). The apparent density was dependent on TPA/TMA ratio and much less than that of linear PBZT (1.57 g/cm^3), showing existence of many nano voids within the network. As the segment was so rigid, many COOH's were left around the voids. The network swelled twice in weight with ε-caprolactam, which was polymerized into a composite form of nylon6 impregnated rigid polymer network. Extraction of free nylon6 from the composite with formic acid showed that a quarter of nylon6 grafted directly to rigid polymer network. The grafted nylon6 could not crystallize evidenced by DSC measurements. On the other hand, particles of PBZT network (several hundred nm in diameter) were prepared by stopping the polycondensation just before gelation. A composite film was prepared with the particles swollen with ε-caprolactam. The ratio of PBZT network/nylon6 was 1/3 and the apparent density of the composite film was 1.23 g/cm^3 which is higher than that of a pure nylon6 film (1.16 g/cm^3). Significant improvement in the mechanical property was observed for this composite.