pentadecafluorooctaoxy)styrene (TF(F15)S) are prepared by nucleophilic substitution of 2,3,4,5,6-pentafluorostyrene. The neat monomers are subjected to atom transfer radical polymerization (ATRP) at 110 °C to high conversions in relatively short times, 10-120 min; TF(F 5)S is additionally polymerized at 70 and 90 °C. Block copolymers with styrene are prepared by the macroinitiator approach. All polymers, in the number-average molecular weight range from 6000 to 35 000, have polydispersity indexes between 1.08 and 1.37. The homopolymers show glass transitions from 16 to 62 °C depending on molecular weight, whereas the block copolymers exhibit phase separation mirrored in two T gs, which could be observed when the smallest block constitutes more than 10 mol %. The fluorinated side chains of P(TF(F5)S) and P(TF(F15)S) enrich the surface of thin films, which results in an advancing water contact angle of 117°and 122°, respectively. Both XPS analyses and contact angle measurements strongly imply that the fluorinated parts of the block copolymers migrate to the surface and create low surface energy films.

A series of anionic P∼O ligands and corresponding palladium-allyl complexes have been synthesized. The latter, along with palladium species formed in situ, were employed for the copolymerization of ethene with functionalized norbornene derivatives. The formed copolymers had high norbornene content (>40 mol %). The systems are highly tolerant of reactive functionalities, and the copolymerizations can even be carried out in the presence of water.

We report the first well-defined palladium-based system for the liVing homopolymerization of ethene, as well as the liVing copolymerization of ethene with carbon monoxide. We demonstrate this by the synthesis of polyethene-block-poly-(ethene-alt-carbon monoxide). In addition, it has been possible to monitor chain growth by sequential insertions of carbon monoxide and ethene into palladium-carbon bonds. The mechanistic studies haVe also allowed us to pinpoint the hitherto not well-understood reason for the general failure to obtain alkene/carbon monoxide copolymers with low carbon monoxide content.