Prominent Spatial Structure and Synergistic Linkage Effects in Bimetallic Titanium Olefin Polymerization Catalysts

Abstract

In this contribution, the binuclear Ti olefin polymerization catalyst 1,4-phenoxy{[Me 2 Si(C 5 H 4 ) 2 ]TiCl} 2 (Complex 2) was synthesized by the reaction of hydroquinone with [Me 2 Si(C 5 H 4 ) 2 ]TiCl 2 . Compared to mononuclear [Me 2 Si-(C 5 H 4 ) 2 ]TiCl 2 (Complex 1), due to the synergistic effect of bimetals, Complex 2 was thermally more stable and showed higher activity up to 1.36 × 10 6 g/(mol Ti h) for ethylene polymerization at 120 °C. Remarkably, adding the phenoxy group in front of the metal center gives the catalyst a denser coordination environment, and the β-H elimination reaction is slowed down, thereby increasing the molecular weight of the polymer. DFT calculations showed that the Ti−Cp distances in active species 2 were extended by 0.059 and 0.063 Å, respectively, compared to those in active species 1. This makes the space of the active center more spacious and easier to promote olefin polymerization. Consequently, the copolymer's 1-octene monomer incorporation rate reaches 16.21 mol %, with a fracture strain of 1140% and a stress recovery (SR) of 65%.

%VBur index and steric maps: from predictive catalysis to machine learning

“…282 This detailed examination underscored the manner in which subtle modifications to the ligand could exert an impact on the stereoselectivity of the propene transformation process, and by extension for 1-decene oligomerization the use of steric maps could unveil the role of group IV diamine bis(phenolate) catalysts. 283 Overall, it must be assessed that quantitatively the use of the concepts of steric maps is frankly focused on ligands such as NHCs, 24,65 but especially the explosion has come in the reproduction of catalytic surfaces where simple polymerization, 284,285 or hydrogenation reactions take place. 31,149…”

“…Overall, it must be assessed that quantitatively the use of the concepts of steric maps is frankly focused on ligands such as NHCs, 24,65 but especially the explosion has come in the reproduction of catalytic surfaces where simple polymerization, 284,285 or hydrogenation reactions take place. 31,149…”