Synthesis of Ultrahigh Molecular Weight Polymers Containing Reactive Functionality with Low PDIs by Polymerizations of Long-Chain α-Olefins in the Presence of Their Nonconjugated Dienes by Cp*TiMe(2)(O-2,6-(i)Pr(2)C(6)H(3))–Borate Catalyst

Copolymerizations of 1-decene (DC) with 1,9-decadiene (DCD), 1-dodecene (DD) with 1,11-dodecadiene (DDD), and 1-tetradecene (TD) with 1,13-tetradecadiene (TDD), using Cp*TiMe(2)(O-2,6-(i)Pr(2)C(6)H(3)) (1)–[Ph(3)C][B(C(6)F(5))(4)] (borate) catalyst in the presence of Al(i)Bu(3)/Al(n-C(8)H(17))(3) proceeded in a quasi-living manner in n-hexane at −30 to −50 °C, affording ultrahigh molecular weight (UHMW) copolymers containing terminal olefinic double bonds in the side chain with rather low PDI (M(w)/M(n)) values. In the DC/DCD copolymerization, the resultant copolymer prepared at −40 °C possessed UHMW (M(n) = 1.40 × 10(6) after 45 min) with low PDI (M(w)/M(n) = 1.39); both the activity and the PDI value decreased at low polymerization temperature (M(n) = 5.38 × 10(5), M(w)/M(n) = 1.18, after 120 min at −50 °C). UHMW poly(TD-co-TDD) was also obtained in the copolymerization at −30 °C (M(n) = 9.12 × 10(5), M(w)/M(n) = 1.51, after 120 min), using this catalyst.