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Polymerizations of 1-decene (DC), 1-dodecene (DD), and 1-tetradecene (TD) by 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 have been explored in the presence of Al cocatalyst. The polymerizations of DC and DD, in n -hexane containing a mixture of Al  i  Bu 3 and Al( n -C 8 H 17 ) 3 , proceeded with high catalytic activities in a quasi-living manner, affording high molecular weight polymers (activity 4120-5860 kg-poly(DC)/mol-Ti·h, M  n for poly(DC) = 7.04-7.82 × 10 5 , after 20 min at -30 °C). The PDI ( M  w / M  n ) values in the resultant polymers decreased upon increasing the ratio of Al( n -C 8 H 17 ) 3 /Al  i  Bu 3 with decreasing the activities at -30 °C. The PDI values also became low when these polymerizations were conducted at low temperatures (-40 or -50 °C); high molecular weight poly(DD) with low PDI ( M  n = 5.26 × 10 5 , M  w / M  n = 1.16) was obtained at -50 °C. The TD polymerization using 1 -borate-Al  i  Bu 3 catalyst (conducted in n -hexane at -30 °C) afforded ultrahigh molecular weight poly(TD) ( M  n = 1.02 × 10 6 , M  w / M  n = 1.38), and the PDI values also decreased with increasing the Al( n -C 8 H 17 ) 3 /Al  i  Bu 3 ratio.

molecules

Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe2(O-2,6-iPr2C6H3)–Borate Catalyst