Complexes of the tetrasodium salt of cobalt(I1)-tetrasulfophthalocyanine and poly(viny1amine) were applied as bifunctional catalysts for the autoxidation of thiols to disulfides. Optical and catalytic experiments gave supporting evidence to the hypothesis, that the isolation of cobalt centers and the catalytic activity can be promoted by increasing the relative amount of polymeric base. It appeared that the specific catalytic activity of the polymeric catalysts depends on the number average degree of polymerization (F,) of the applied polymer samples. In particular at relatively high cobalt content, samples with comparatively low Fn give more protection against aggregation of cobalt sites (i.e. inactivation) and, therefore, effect a higher specific catalytic activity. A statistical calculation, suitable to determine the distribution of cobalt sites over the polymeric coils, supports the interpretation of the experimental data.

Macroporous highly crosslinked styrene(St)-divinylbenzene(DVB) copolymers were prepared by solution and suspension polymerization techniques. The obtained materials allowed the grafting of poly(N-vinyl-tert-butylcarbamate) (PVCa) either by addition of VCa macroradicals to the solid bound double bonds or by termination involving the reaction of VCa macroradicals with radicals present on the carrier. Poly(viny1amine) (PVAm) grafted on St-DVB carriers was obtained after the hydrolysis of grafted PVCa with HCl and the subsequent removal of the aminebonded HCI by means of NaOH. Heterogeneous bifunctional catalysts were obtained by attachment of cobalt(I1) 4,4 ',4 ",4"'-tetracarboxyphthalocyanine (CoPc(COOH),)to the grafted PVAm. The prepared catalysts were applied to the autoxidation of thiols to disulfides, both in predominantly apolar media and in aqueous media. It was demonstrated, that important prerequisites for the applicability of macroporous St-DVB copolymers as carriers for the PVAm-CoPc(COOH), catalyst include a high surface area, a sufficiently large average pore diameter and accessibility of the pendent double bonds. ZUSAMMENFASSUNG: MakroporBse hochvernetzte Copolymere aus Styrol (St) und Divinylbenzol (DVB) wurden durch LBsungs-und Perlpolymerisation hergestellt. Die dargestellten Triiger erm8glichten die Pfropfung von Poly(N-vinyl-tert-butylcarbamat) (PVCa) entweder durch Addition von VCa-Makroradikalen an die am unI8slichen Triiger anhangenden Doppelbindungen oder durch Termination von VCa-Makroradikalen rnit Radikalen, die sich an der Trageroberfllche befinden. Poly(viny1amin) (PVAm) gepfropft auf St-DVB Trager wurde durch Hydrolyse von gepfropftem PVCa mit HCI und nachfolgende Entfernung von amingebundenem HCI mittels NaOH erhalten. Heterogene bifunktionelle Katalysatoren wurden dargestellt durch Bindung von Kobalt(I1) 4,4',4",4"'-tetracarboxyphthalocyanin (CoPc(COOH),) an gepfropftes PVArn. Die hergestellten Katalysatoren wurden zur Oxidation von Thiolen zu Disulfiden, sowohl in vorwiegend apolaren als auch in wurigen Ldsungsmitteln verwendet. Es wurde bewiesen, daI3 eine groDe innere Oberflkhe, ein hinreichend grol3er mittlerer Porendurchmesser und Zuglnglichkeit der anhlngenden Doppelbindungen wichtige Voraussetzungen sind fur die Anwendbarkeit vom makropordsen St-DVB Copolymeren als Trlger fur den PVAm-CoPc(COOH), Katalysator.