Studies on Control of the Microvoids Fixed in Non-eguilibrium Glassy State

在这项研究中，我们试图澄清高分子膜的高有序结构和气体传输性能之间的关系，以建立控制的微孔。本文首先研究了在不同压力下用CO_2调节膜的未松弛体积，使其变化的高分子膜的气体吸附性能。观察到吸附量的增加，可以说未松弛体积随调理压力增加而增加。经CO_2处理后，样品的~1H-NMR化学位移发生了上移，峰宽变窄。<129>其次，我们制备了具有刚性侧链的脂环族和芳香族聚酰亚胺，讨论了侧链作为一种附加因素对气体传输性能和分子结构的影响。结果表明，主链的刚性和平直度是控制气体渗透性的重要因素。M的影响 ...更多信息 研究了棒状聚酰亚胺（BP）/半柔性聚酰亚胺共混膜的相容性对气体传输性能的影响。所有的共混膜的渗透系数大于预期的半对数加和规则。对聚甲基丙烯酸甲酯/苯乙烯-丙烯腈共聚物共混体系也得到了同样的结果。此外，我们还研究了一些结晶聚合物的气体输运性质，因为晶体可以被看作是完全受控的微孔之一。在聚-4-甲基戊烯-1的情况下，一些气体渗透到比体积大于非晶相的结晶相中。退火后的间规聚苯乙烯铸膜的双吸附参数降低结晶度的增加，表明吸附的溶剂的吸附形成的网站。从吸附量、热稳定性等方面看，间规聚苯乙烯与几种芳香族溶剂形成络合物的情况各不相同

In this study, we tried to clarify the relationship between the high-ordered structures of polymeric membranes and the gas transport properties in order to establish the control of the microvoids. At first, the gas sorption properties of polymeric membranes whose unrelaxd volume was varied by conditioning with CO_2 at various pressures, were studied. The increase in the amount of sorption was observed, it can be said that the unrelaxd volume increased with the conditioning pressure. The CO_2-conditioning was carried out, ^<129>XeNMR chemical shifts of the Xe in the conditioned samples showed up-field shift and their peak widths became narrow. Next, we prepared the alicyclic and aromatic polyimides with rigid side chain to discuss the effect of the side chain on gas transport properties and molecular structure, as an additive factor. It was concluded that the rigidity and straightforwardness of the main chain was the very important factor to control the gas permeability. The effect of m … More iscibility on gas transport properties of the rodlike polyimide (BP) /semi-flexible polyimide blend membranes were studied. The permeability coefficients of all the blend membranes were larger than those expected from the semilogarithmic additivity rule. The same results were obtained for poly (methyl methacrylate) /poly (stirene-co-acrylonitrile) blend system. Furthermore, we studied the gas transport properties of some crystalline polymers, because the crystal could be seen one of the completely controlled microvoids. In the case of poly-4-methylpentene-1, the some gases permeate in the crystalline phase whose specific volume is larger than that of the amorphous phase. The obtained dual-sorption parameter for the annealed syndiotactic polystirene cast membrane was lowered by the increase of crystallinity, indicating the sorption site formed by the adsorption of the solvent. The complex formation of the syndiotactic polystirene with some aromatic solvents were different among them from viwpoints of the sorption amounts, thermal stability, and so on. From these study, the Less