Poly(norbornene carboxylic acid ester)s: Synthesis and properties

The vinylic polymerization of 5‐norbornene‐2‐carboxylic esters with different palladium catalysts to polymers of high molecular weights is reported. Computer simulations based on a force field approach show that these polymers display a rigid statistical chain conformation and are thus a further example of rotationally strongly constrained polymers. The polymers are soluble in a variety of solvents despite their rigidity, they are amorphous, possess glass transition temperatures well above 250°C, and have a high packing density. The dipoles located in the lateral groups perform a secondary relaxation process similar to the case of flexible or rigid rod‐like polymers containing ester groups.