Dynamics and Interfacial Property of Polymers Super-saturated with Oxygen

氧分子在高聚物基体中的溶解度是大分子复合物中物理溶解氧的上百倍，这是由于氧分子在高聚物基体中的化学专一性、快速性和可逆性结合。从高分子气固界面氧的比吸附、氧在高分子基体上的表面扩散以及与氧溶解共轭的高分子性质等方面研究了氧超饱和聚合物的特性。(1)用Langmuir和亨利等温线估算并分析了25 ℃空气气氛下固载钴卟啉聚合物的溶解氧量为3cm ^3（STP）/g（聚合物）。氧结合反应受卟啉化学修饰结构的控制，这与超大量和快速的氧吸附动力学有关。(2)首次在孔表面修饰钴卟啉的多孔膜上观察到氧的二维表面扩散。该膜具有> 10^4Barrers的高渗透性和对氧-2的选择性渗透。利用一个包含氧气表面扩散和气相扩散的平行模型对氧气的增强扩散和特定扩散进行数学分析，得出表面扩散层的渗透率为-10^3 Barrers，氧气的表面扩散常数为10^<-4>cm ^2 s^<-4>。(3)在特定氧压下，含柳珊瑚碱微晶的聚合物的氧吸附量与氧分压的关系呈陡峭或非连续增大。这种特定的和开关型或S形型的氧吸附是可逆的，反复观察。与滞后等温线相关联的特定氧吸附行为与氧结合部分的晶体微观结构和在聚合物基质中的弛豫的协同作用进行了讨论。

Molecular oxygen is dissolved into pokymer matrixes more than hundred times of the physically dissolved oxygen for macromolecular complexes, which is ascribed to chemically specific, rapid, and reversible oxygen-binding to the compelex moieties. Characteristics the polymers super-saturatrd with oxygen was first studied in view points of specific oxygen sorption at the gas-solid polymer interface, surface diffusion of oxygen on the polymer matrixes, and polymer property conjugated with the oxygen dissolution.(1) Dissolved oxygen amount 3cm^3 (STP) /g (polymer) (at 25ﾟC under air atmosphere) into solid-atate cobaltporphyrin-bound polymers was estimated and analyzed with Langmuir's and Henry's isotherms. Oxygen-binding reactivity was controlled with the chemically modified structure of porphyrin, which was related to extra-large amount and rapid kinetics of oxygen sorption.(2) Two-dimensional of surface diffusion of oxygen was first observed on a porous membrane modified on its pore surface with cobaltporphyrin. The membdrane displayd high permeability >10^4 Barrers and permselectively for oxygen -2. The enhanced and specific diffusion of oxygen was mathematically analyzed with a parallel model involving surface diffusion of oxygen and gas phase diffusion, to yield permeability -10^3 Barrers for the surface diffusion layr and surface diffusion constant of oxygen 10^<-4> cm^2 s^<-4>.(3) Oxygen sorption amount-oxygen partial pressure relationship was steeply or non-continuously augmented at a specific oxygen pressure for the polymers involving micro-crystals of salcomine. This specific and on-off-type or sigmoidal-type oxygen sorption was reversibly and repeatedly observed. The specific oxygen sorption behabiour associated with a hysterisis isotherm was discussed with a cooperative interaction of crystal micro-structure of the oxygen-binding moiety and relaxation in the polymer matrix.