Molecular Weight and End Group Control of Isotactic Polystyrene Using Olefins and Nonconjugated Diolefins as Chain Transfer Agents

Styrene was isospecifically polymerized on dichloro[1,4-dithiabutandiyl-2,2‘-bis(6- tert -butyl-4-methylphenoxy)]titanium ( 1 ) activated with methylaluminoxane in the presence of monoolefins such as 1-hexene, cyclopentene, and norbornene and nonconjugated diolefins such as 1,9-decadiene, 1,7-octadiene, and dicyclopentadiene. The molecular weight of isotactic polystyrene was varied from 2000 to 600 000 g/mol as a function of the olefin/styrene molar ratio without sacrificing high catalyst activities. Chain transfer constants were determined, with the highest values found for linear mono- and nonconjugated diolefins. In contrast to norbornene, 1-olefin incorporation was very low. End groups were identified by means of 13 C NMR investigations of polymers containing 13 C-labeled 1-octene. Olefin- and diolefin-terminated isotactic polystyrenes including novel vinyl-terminated macromonomers were obtained in high yields.