Metathesis-type poly-exo-tricyclononenes with fluoroorganic side substituents: Synthesis and gas-transport properties

Abstract The synthesis and gas-transport properties of new metathesis-type polynorbornenes bearing fluoroorganic side groups are reported. The necessary monomers, fluorosubstituted exo -norbornene derivatives ( exo -tricyclononenes), were obtained using one-step method based on stereo- and regioselective [2 + 2+2]-cycloaddition of quadricyclane and fluoroalkenes. A set of high molecular weight polymers with different side groups were prepared from the synthesized F-substituted exo -tricyclononenes over the 1-st generation Grubbs catalyst. Permeability and diffusion coefficients of various gases (He, H 2 , O 2 , N 2 , CO 2 , CH 4 ) in these poly- exo -tricyclononenes were determined for the first time and new relationships between polymer structure and gas permeability were established. Metathesis poly- exo -tricyclononene bearing four CF 3 -groups in each monomer unit displayed the highest gas permeability for the tested gases among metathesis polynorbornenes with F-organic substituents reported so far.