Dynamics and Interfacial Property of Polymers Super-saturated with Oxygen

分子氧被溶解到聚合物基质中，是大分子络合物物理溶解氧的数百倍以上，这归因于分子氧与复杂结构部分的化学特异性、快速和可逆性的氧结合。从聚合物在气固界面上的比氧吸附、氧在聚合物基质上的表面扩散以及聚合物性质与氧溶解的耦合等方面对聚合物的氧过饱和特性进行了首次研究：(1)估算了25ﾟ℃空气气氛下聚合物中3 cm~3(STP)/g(聚合物)的溶解氧量，并用朗缪尔和亨利等温式进行了分析。氧键结合反应由卟啉的化学修饰结构来控制，这与其超大的吸氧量和快速的吸氧动力学有关。(2)首次观察到氧在表面修饰的多孔膜上的二维表面扩散。Membdrane显示出高渗透性&10^4阻挡层，对氧-2具有渗透选择性。用氧的表面扩散和气相扩散的并行模型对氧的强化扩散和比扩散进行了数学分析，得到了氧的表面扩散层渗透率为-10^3 Barrers，氧的表面扩散常数为10^2 S。(3)在特定的氧分压下，含有海可明微晶的聚合物的氧吸附量-氧分压关系急剧或非连续地增大。这种特定的和开关类型或S形类型的吸氧是可逆的和重复的。结合聚合物基质中氧结合部分的晶体微结构与弛豫的协同作用，讨论了与滞后等温线有关的特定吸氧行为。

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.