Xiao Youchang, Chung Tai-Shung, Chng Mei Lin
Department of Chemical & Biomolecular Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore.
Langmuir. 2004 Sep 14;20(19):8230-8. doi: 10.1021/la049060z.
6FDA-polyimide films modified by polyamidoamine (PAMAM) dendrimers with generations of 0, 1, and 2 are reported in this article. The actual molecular conformation and bulk size of these three generation dendrimers immobilized on polyimide surface were characterized by atomic force microscopy. After comparing with the results of dynamic simulation, we believe that the disk-shape cluster structure of dendrimers has been developed on the polymer surfaces. The amidation and cross-linking reaction between dendrimers and polyimide were examined and quantified by X-ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, and gel content measurements. Modification time and the generations of PAMAM dendrimer have been verified as two important factors in determining the properties of modified polyimide films. These modified polyimide films exhibit excellent gas separation performance. The ideal selectivity of He/N(2) increases tremendously to about 200% as compared to that of the original polyimide film. Particularly, the separation performance of CO(2)/CH(4) gas pair can be improved beyond the upper bond limit possibly due to the strong interactions of dendrimer molecules with CO(2), which was verified by sorption tests.
本文报道了由0代、1代和2代聚酰胺-胺(PAMAM)树枝状大分子改性的6FDA-聚酰亚胺薄膜。通过原子力显微镜对固定在聚酰亚胺表面的这三代树枝状大分子的实际分子构象和整体尺寸进行了表征。与动态模拟结果比较后,我们认为树枝状大分子的盘状簇结构已在聚合物表面形成。通过X射线光电子能谱、衰减全反射傅里叶变换红外光谱和凝胶含量测量对树枝状大分子与聚酰亚胺之间的酰胺化和交联反应进行了检测和定量。已证实改性时间和PAMAM树枝状大分子的代数是决定改性聚酰亚胺薄膜性能的两个重要因素。这些改性聚酰亚胺薄膜表现出优异的气体分离性能。与原始聚酰亚胺薄膜相比,He/N₂的理想选择性大幅提高至约200%。特别地,CO₂/CH₄气体对的分离性能可能由于树枝状大分子分子与CO₂的强相互作用而提高到超出上限,这已通过吸附测试得到证实。