In situ catalyst systems for ring‐opening metathesis polymerization

Several new in situ tungsten catalyst systems for ring-opening metathesis polymerizations (ROMP) by reaction injection molding (RIM) have been developed by adding BF3 promoter to binary catalyst systems, by using metal hydride cocatalysts, and by altering the ligands on the procatalyst metal center. BF3 etherates improved catalyst efficiency and reduced induction times for formation of active catalysts from reaction of aryloxytungsten complexes [e.g., (ArO)y(WXx)] with organotin hydrides. Coordinatively unsaturated cationic intermediates, such as [(ArO)yWXx-1]+ BF3X−, are proposed to facilitate formation of the active catalysts. Tougher poly(dicyclopentadiene) (polyDCPD) composites were produced using < 5 wt % of styrene-butadiene block copolymers due to formation of small “shell-core” rubber morphologies when BF3 promoter was added to the catalyst system. Nonalkylating metal hydrides besides R3SnH, including (PPh3)2CuBH4, (PPh3CuH)6, and Cp2ZrClH, were shown to be cocatalysts. The optimum 2 : 1 stoichiometric ratio of organotin hydride cocatalyst to tungsten, revealed by BF3-promoted catalyst systems, and WV EPR resonances (g ∼ 1.7) observed in the reaction of aryloxytungsten with organotin hydride are consistent with an overall reduction and reoxidation mechanism for formation of the active metathesis catalysts. Some tungsten complexes derived from 9-hydroxyfluorene, 2,2′-(and 4,4′)-biphenols, and 1,4-hydroquinones were found to be very reactive procatalysts, even in the absence of cocatalyst in some cases. These procatalysts also were paramagnetic, characterized by unusual EPR spectra consistent with WV (g = 1.6–1.9) and “ligand-centered” (g = 2.003) resonances. Valence tautomeric species, analogous to catecholate-semiquinonate complexes, are proposed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3027–3047, 1997