Dynamics and Interfacial Property of Polymers Super-saturated with Oxygen

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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.