Design of functionalized cyclic aryl ethers and alkenes and their subsequent ring-opening polymerization

Abstract

The ring-opening polymerization of a variety of cyclic and bicyclic monomers that were prepared via nucleophilic aromatic substitution reactions mediated by the cyclopentadienyliron moiety was explored. The ability to design structurally different monomers using this approach, allowed for the isolation of polymeric materials with different chemical and physical properties. It has been well established that organoiron complexes containing an assortment of functionalities can be prepared using this methodology. A variety of asymmetric cyclic aryl ethers were prepared following reaction of diiron complexes with a dinucleophile. Following cleavage of the metal moieties, the aromatic macrocycles were converted to the corresponding insoluble polyaromatic ethers via ring-opening polymerization in the presence of an anionic initiator. The ring-opening metathesis polymerization of a series of bicyclo[2.2.1]heptenes was also investigated. Two classes of polynorbornenes containing cationic iron moieties within their side chains were synthesized u ing organoiron chemistry, and subsequently polymerized in the presence of ruthenium-based catalyst. The resulting organometallic polynorbornenes, with terminal or lateral side chains displayed excellent solubility and thermal stability.