Ultrasonic spectroscopic evaluation of the ring‐opening metathesis polymerization of dicyclopentadiene

An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol^?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003     

Preparation of cadmium selenide-polyolefin composites from functional phosphine oxides and ruthenium-based metathesis

Cadmium selenide nanoparticles, prepared by known methods, were stabilized with functional phosphine oxide 1, then used to support the polymerization of cyclic olefins radially outward from the surface by ruthenium-catalyzed ring-opening metathesis polymerization (ROMP). The conversion of compound 1 into the new metathesis catalyst 3 by carbene exchange and the subsequent polymerization of cyclic olefins were observed spectroscopically by (1)H NMR to afford for example CdSe-polycyclooctene composite 6. Transmission electron micrographs on thin films of these composites showed good nanoparticle dispersion. This is in stark contrast to the substantial nanoparticle aggregation observed when similar polymerizations were performed in the presence of conventional TOPO-covered nanoparticles. The methods reported here to prepare composite product 6 are applicable to other cyclic olefins, and suggest that this chemistry will be useful for incorporating CdSe nanoparticles into a wide variety of polymer matrices.