Polystyrene-metalloporphyrins

Abstract Pressure-sensitive paint (PSP) is applied to the areodynamics measurement. PSP is optical sensor based on the luminescence of dye probe molecules quenching by oxygen gas. Many PSPs are composed of probe dye molecules, such as polycyclic aromatic hydrocarbons (pyrene, pyrene derivative etc.), transition metal complexes (ruthenium(II), osumium(II), iridium(III) etc.), and metalloporphyrins (platinum (II), palladium(II), etc.) immobilized in oxygen permeable polymer (silicone, polystyrene, fluorinated polymer, cellulose derivative, etc.) film. Dye probe molecules adsorbed layer based PSPs such as pyrene derivative and porphyrins directly adsorbed onto anodic oxidised aluminium plat substrate also developed. In this section the properties of various oxygen permeable polymer for matrix and various dye probes for PSP are described. 

Ionic meso-tetraarylporphyrins can be bound to a range of charged supports including cross-linked polystyrene based anions,78 cations,79 exchange resins, cross-linked and quaternized poly(4-vinylpyridine)80 and the oxides of silica, alumina and magnesia.81 Metalloporphyrins may be attached to supports by coordination of a ligand on the support to the metal centre. Such catalysts mimic... 

Rollman (4 3) synthesized a series of polymer-bonded metalloporphyrins. Functionalized tetraphenyIporphyrines were attached to porous polystyrene resins via amine, carbonyl and ester linkages and metal ions (Co,Ni,Cu,Zn) were then incorporated into the structures. The porphyrin polymers that contained both oxidation (Co) and proton-acceptor sites (amine and carboxylate groups) were effective catalysts for the oxidation of thiols to disulfides. When the catalyst was exposed to a refinery stream containing only 180 ppm mercaptan sulfur, deactivation occurred. Deactivation was thought to occur via oxidation of the porphyrins by free radicals known to be present in such catalytic systems. 

Porphyrins. Rollmann (21) has described the preparation of a variety of metalloporphyrins on a macroretlcular polystyrene copolymer with either divinylbenzene or ethylene glycol dimethacrylate. Polymer attachment could be made through an amine ester or ketone linkage. Cobalt(III) derivatives catalyze the oxidation of thiols in air. The polymers did show a marked tendency to age with resultant loss of activity. 

Oxone has also been used in the metalloporphyrin-catalyzed diastereoselective epoxidation of allyl-substituted alkenes (eq 109) and in the manganese, salen-polystyrene-bound imidazole catalyzed deoxidation of alkenes (eq 110). ... 

The activity of the liquid phase polyhalogenated metalloporphyrins (Co, Mn, Fe) and supported catalysts (silica, polystyrene) and the cationic metalloporphyrins encapsulated in NaX zeolite are founded to be active for cyclooctane oxidation with molecular into ketone and alcohol with primary ketone formation. At the last case the ration c-one/c-ol is higher than at the use supported on silica and polystyrene catalysts and in fact coincide with results, which are received with the cationic metalloporphyrins in solution. [54]. 

---