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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.

polymers

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*TiMe2(O-2,6-iPr2C6H3)–Borate Catalyst