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-26-iPr2C6H3)–Borate Catalyst

摘要

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 (O-2,6- Pr C H ) ( )–[Ph C][B(C F ) ] (borate) catalyst in the presence of Al Bu /Al( -C H ) proceeded in a quasi-living manner in -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 ( / ) values. In the DC/DCD copolymerization, the resultant copolymer prepared at −40 °C possessed UHMW ( = 1.40 × 10 after 45 min) with low PDI ( / = 1.39); both the activity and the PDI value decreased at low polymerization temperature ( = 5.38 × 10 , / = 1.18, after 120 min at −50 °C). UHMW poly(TD- -TDD) was also obtained in the copolymerization at −30 °C ( = 9.12 × 10 , / = 1.51, after 120 min), using this catalyst.