THERMALINDUCED AND PHOTOINDUCED RING-OPENING METATHESIS POLYMERIZATION (ROMP) (PROMP) - AN EFFICIENT TOOL IN POLYMER CHEMISTRY/

Properties and applications of newly developed homogeneous ring-openin g metathesis polymerization catalysts as well as photoinduced ring-ope ning metathesis polymerization catalysts are discussed. It is shown th at simple alkyl complexes, e.g. [W(=NPh)(CH2SiMe3)(3)Cl] as well as [R u(arene)(2)](2+) or [Ru(NC-R)(6)](2+) complexes act as one-component P hoto-ROMP initiators. Catalysts with good thermal latency are describe d for both classes. High quantum yields are observed for the photochem ically induced solvation of Ru(II) complexes. Polymer structure and ki netic aspects of the reaction are consistent with [Ru(solvent)(6)](2+) acting as the catalytically active species. The mechanism of aqueous ROMP with Ru(IT) salts is discussed, which differs considerably from t he classical ROMP reaction with Schrock-type catalysts in the sense th at it is a chain reaction and not a living polymerization. Home-and co polymers using exo-oxa-norbornene-carboximide ester derivatives were p repared with the ROMP technology and used, inter alia, to formulate ve ry sensitive positive tone high-resolution microresists. (C) 1997 Else vier Science S.A.