Abstract
Properties and applications of newly developed homogeneous ring-opening metathesis polymerization catalysts as well as photoinduced ring-opening metathesis polymerization catalysts are discussed. It is shown that simple alkyl complexes, e.g. [W(NPh)(CH 2SiMe 3) 3Cl] as well as [Ru(arene) 2] 2+ or [Ru(NC–R) 6] 2+ complexes act as one-component Photo-ROMP initiators. Catalysts with good thermal latency are described for both classes. High quantum yields are observed for the photochemically induced solvation of Ru(II) complexes. Polymer structure and kinetic aspects of the reaction are consistent with [Ru(solvent) 6] 2+ acting as the catalytically active species. The mechanism of aqueous ROMP with Ru(II) salts is discussed, which differs considerably from the classical ROMP reaction with Schrock-type catalysts in the sense that it is a chain reaction and not a living polymerization. Homo- and copolymers using exo-oxa-norbornene-carboximide ester derivatives were prepared with the ROMP technology and used, inter alia, to formulate very sensitive positive tone high-resolution microresists.
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