Half-sandwiched titanocene trichloride (Cp′TiCl3; Cp′ = cyclopentadienyl, Cp; pentamethylcyclopentadienyl, Cp*; indenyl, Ind) combined with an alkylaluminum (triisobutylaluminum, diisobutylaluminum hydride, or trioctylaluminum)/Ph3CB(C6F5)4 cocatalyst system has been examined for polymerization of styrene. Syndiospecific polymerization of styrene proceeded under limited polymerization conditions. The maximum productivity of syndiotactic polystyrene was attained under the following conditions: Al/Ti molar ratio = 20 (mol/mol), polymerization temperature = 40-50 °C. The nature of alkylaluminum compounds and the ligand structure of the catalysts affected the range of the polymerization temperature in which proceeds the syndiospecific polymerization of styrene.
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