No abstract

An investigation was carried out on branching of polymers obtained by lauroyl-peroxide or by radiation-initiated polymerization of vinylchloride. As a result, branching shows no dependence on conversion and could be ascribed, a t least partially, to the presence of CHzC1-side groups.A reaction mechanism for this type of branching was proposed. ZUSAMMENFASSUNG:Es wurde die Verzweigung van durch Lauroylperoxid oder Bestrahlung initiiertem Polyvinylchlorid untersucht. Dabei zeigte sich, dal3 der Umsatz keinen Einflul3 auf die Verzweigung hat. Diese durfte, zumindest teilweise, seitlichen CHzC1-Gruppen zuzuschreihen sein.Es wird ein Reaktionsmechanismus fur eine solche Art der Verzweigung vorgeschlagen.

Four synthetic ion-exchange resins (AH, BH, CH, DH) of different hydrophilic/hydrophobic properties were used as supports for heterogeneous palladium catalysts (A, B, C, D). The resins contained styrene (STY) and 2-(methacryloxy)ethylsulfonic acid (MESA) as the comonomers. Either divinylbenzene (DVB: CH, DH resins) or N,N'-methylenebisacrylamide (MBAA: AH, BH resins) were used as the cross-linker. AH contained also N,N-dimethylacrylamide (DMAA) as the third comonomer. The catalysts (Pd 0.25-0.45% w/w) were obtained by ion-exchanging the acidic forms of the resins with [Pd(OAc)2] and reducing palladium(II) with excess sodium borohydride. The use of NaBH4 also ensured the neutralization of the acidic sites of the supports. No effect of the hydrophilic/hydrophobic properties of the supports was observed in the hydrogenation of cyclohexene and 2-cyclohexen-1-one in methanol, at 25 degrees C and 0.5, 1, and 1.5 MPa, respectively. However, catalysts A and B, containing amido groups provided by either DMAA or MBAA, proved to be more active than C and D. The observed activity enhancement was directly proportional to the nitrogen/ palladium molar ratio in the catalysts. This finding suggests that amido groups promote palladium through a direct interaction with the metal surface.