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Summary: Fluorinated bis(phenoxy‐imine)Ti complexes 1–3 combined with MgCl2/i‐BunAl(OR)3−n (MgCl2‐supported catalysts) were able to polymerize propylene in a living fashion at room temperature to provide slightly to highly syndiotactic poly(propylenes) (PPs) with extremely narrow distributions of molecular weight. These represent the first examples of MAO‐ and borate‐free group 4 metal‐based living catalysts. The supported complexes 2 and 3 formed PPs with higher syndiotacticity and Tm's than the corresponding homogeneous MAO‐activation systems (e.g., 3: rr 97%, Tm 155 °C; MAO activation: rr 93%, Tm 152 °C). The measured Tm of 155 °C represents the highest known Tm for syndiotactic PPs synthesized at room temperature. Polymerization of propylene to poly(propylene) with supported Ti‐based catalysts. image Polymerization of propylene to poly(propylene) with supported Ti‐based catalysts.
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Nakayama et al. (2005) studied this question.
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