Alternating copolymerization and terpolymerization of vinyl‐substituted phenolic antioxidants with propene and carbon monoxide by a palladium( II )‐based catalyst: polyketones containing intramolecular stabilizers

The copolymerization and terpolymerization reactions of the vinyl‐substituted phenolic stabilizers, 6‐ tert ‐butyl‐2‐(1,1‐dimethylhept‐6‐enyl)‐4‐methylphenol, o ‐allylphenol, 4‐methylstyrene‐2,6‐di‐ tert ‐butylphenol and 2,6‐di‐ tert ‐butyl‐4‐allylphenol, with propene and carbon monoxide, by using the solvent‐stabilized palladium( II ) phosphine complex [Pd(dppp)(NCCH 3 ) 2 ](BF 4 ) 2 (dppp, 1,3‐bis(diphenylphosphino)propane) as a catalyst precursor and methanol as a co‐catalyst, is described. The influence of functional α‐olefins/CO units, distributed statistically along the propene/carbon monoxide (P/CO) copolymer backbone, on the molecular weight, glass transition temperature ( T g ), elastic behavior and stability of the high‐molecular‐weight P/CO copolymer has been investigated. Loss of both elasticity and transparency were observed upon incorporating o ‐allylphenol as a termonomer. The terpolymers, which contain phenolic stabilizers, were shown to be more stable when compared to the stabilizer‐free polyketones. In contrast to the propene/carbon monoxide copolymer, no degradation was observed for the 2,6‐di‐ tert ‐butyl‐4‐allylphenol/P/CO terpolymer; instead, the molar masses increased. Copyright © 2004 Society of Chemical Industry