Abstract
The Ring Opening Metathesis Polymerization (ROMP) of a series of cyclic alkenes bearing heteroatom functionality has been performed using a classical WCl~6~‐based catalyst system. All of the alkenes studied exhibited significantly slower polymerization rates compared with the hydrocarbon monomer dicyclopentadiene (DCPD), this being most pronounced for monomers containing a tertiary nitrogen atom substituted at the 2 position of the norbornene skeleton. Cyclic alkene anhydrides, prepared by the Diels‐Alder addition of cyclopentadiene to maleic and itaconic anhdrides, were found to be polymerizable with high yields giving cross‐linked polymers which exhibited very high glass transition temperatures. Monofunctional cyclic imide derivatives of the cyclopentadiene‐itaconic anhydride adduct were found to be polymerizable to moderate molecular weight thermoplastic materials with high glass transition temperatures, whilst difunctional cyclic imide derivatives led to cross‐linked thermoset polymers. The solution copolymerizations of the cyclopentadiene‐maleic anhydride adduct with DCPD, and of a cyclic imide derivative of the cyclopentadiene‐itaconic anhydride adduct with DCPD, were carried out to form copolymers in high yields having glass transition temperatures intermediate between those of the respective homopolymers.