Polar Isotactic and Syndiotactic Polypropylenes by Organozirconium‐Catalyzed Masking‐Reagent‐Free Propylene and Amino–Olefin Copolymerization

Polar functionalized isotactic and syndiotactic polypropylenes (PPs) are synthesized by direct, masking‐reagent‐free propylene and amino–olefin (AO, CH2=CH(CH2)xNnPr2, x=2, 3, 6) copolymerizations using the activated precatalysts rac‐[Me2Si(indenyl)2]ZrMe2 and [Me2C(Cp)(fluorenyl)]ZrMe2, respectively. Polymerization activities at 25 °C are as high as 4208 and 535 kg/(mol h atm) with AO incorporation up to 4.0 mol % and 1.6 mol %, respectively. Remarkably, introducing the amino‐olefin comonomers significantly enhances stereoselection for both isotactic (mmmm: 59.5 %→91.0 %) and syndiotactic (rrrr: 66.3 %→81.3 %) products.