This paper describes palladium (II) catalyst based synthesis and detailed characterization of vinyl-type polynorbornenes (PNBs) with bulky phenyl, adamantane, or norbornane substituents linked by ester, ether, or alkyl bridges. The structure–property relationships of the substituted PNBs were investigated concerning the thermal stability, glass transition temperature, wide-angle X-ray scattering (WAXS) patterns, mechanical properties, and ...