Regioselective partial hydrogenation of tricyclopentadiene (TCPD) was achieved with a high turnover number of 10000 by catalysis with a N-heterocyclic carbene palladium complex.
Copolymerization of ethylene and the partially hydrogenated product, dihydrotricyclopentadiene (HTCPD), was realized using a catalytic system of [8-(？？5-C5Me4)-2-Me(C9H8N)-？？N]TiMe2 (C9H10NH = 1,2,3,4-tetrahydroquinoline) activated with (Ph3C)+[B(C6F5)4]-. The copolymer was unambiguously characterized through the analysis of one- and two-dimensional NMR spectra. The monomer reactivity ratios, rethylene and rHTCPD, determined through the Fineman-Ross plot, were 2.8 and 0.025, respectively, indicating negligible successive insertion of two HTCPD. A nearly alternating copolymer with a HTCPD content of 45 mol% was obtained with a satisfactory activity (4.7 ？~106 g/molTi⋅h), of which Tg was 177oC, significantly higher than that of norbornene/ethylene copolymer at the same cycloolefin content. Tensile stress-strain curves indicated that the brittleness observed for a high Tg norbornene/ethylene copolymer was relieved to show some ductile property for the HTCPD/ethylene copolymer of the same level of high Tg.
