Influence of ruthenium alkylidene complexes bearing tricyclohexylphosphine or 3-bromopyridine ligand on the properties of fluorine containing polymers

The catalytic performance of ruthenium alkylidene complexes bearing tricyclohexylphosphine or 3-bromopyridine ligand in the ring opening metathesis polymerization (ROMP) of fluorine containing monomers, exo-N-4-fluorophenyl-7-oxanorbornene-5,6-dicarboximide (FPhONDI) and exo-N-4-fluorophenyl-norbornene-5,6-dicarboximide (FPhNDI) was investigated. Pure monomers were subjected to ROMP with RuCl₂(PCy₃)₂(CHPh) (I), RuCl₂(PCy₃)(H₂IMes)(CHPh) (II), RuCl₂(3-Br-py)₂(PCy₃)(CHPh) (III) and RuCl₂(3-Br-py)₂(H₂IMes)(CHPh) (IV). The polymers were fully characterized using NMR, DSC, SEM and GPC. Catalysts I–IV displayed significant ROMP activity, allowing for the synthesis of the corresponding polymers with polydispersity indices (PDIs) in the range of 1.4–4.0. High molecular weight polymers (Mw up to 4.95 x10⁵) were prepared in yields up to 90 %, depending on the initiator and monomer used.