Functional poly(1,4-ketone)s with pendant hydroxy moieties, 1 - Pd(II)-catalyzed alternating copolymerization of carbon monoxide and allylbenzene derivatives

Functional poly(1,4-ketone)s were prepared by alternating copolymerization of carbon monoxide with substituted allylbenzenes, namely 2-allylphenol 1, 2-allyl-4-methylphenol 2, 2-allyl-6-methylphenol 3, 2-allylmethoxybenzene 4 ,2-allylethoxybenzene 5, 2-allylacetoxybenzene 6 and 4-allylmethoxybenzene 7. The dicationic Pd(II) bis(phosphine) complex [Pd(DPPP)(CH3CN)(2)] (BF4)( 2) 10 [DPPP = 1,3-bis(diphenylphosphino)propane] was used as the catalyst p recursor. Optimum results occurred with monomers that bear oxygen-containin g substituents located in ortho-position to the allyl group. Copolymers der ived from phenolic monomers structurally differ from their protected analog ues because they predominantly display ketalic character due to nucleophili c attack of the OH groups towards neighbored keto moieties, Pendant hydroxy moieties of functional poly(1,4-ketone)s were reacted with chlorides and a nhydrides of carboxylic acids to form the corresponding esters as a model r eaction for grafting processes. Furthermore, isocyanates were used in terms of post-polymerization functionalization. [GRAPHICS] Dependence of molecular weight and copolymer yield on the acivator concentr ation in the alternating copolymerization of CO and 1.