This contribution reports the discovery and application of phenoxy-imine-based catalysts for olefin polymerization. Ligand-oriented catalyst design research has led to the discovery of remarkably active ethylene polymerization catalysts (FI Catalysts), which are based on electronically flexible phenoxy-imine chelate ligands combined with early transition metals. Upon activation with appropriate cocatalysts, FI Catalysts can exhibit unique polymerization catalysis (e.g., precise control of product molecular weights, highly isospecific and syndiospecific propylene polymerization, regio-irregular polymerization of higher alpha-olefins, highly controlled living polymerization of both ethylene and propylene at elevated temperatures, and precise control over polymer morphology) and thus provide extraordinary opportunities for the syntheses of value-added polymers with distinctive architectural characteristics. Many of the polymers that are available via the use of FI Catalysts were previously inaccessible through other means of polymerization. For example, FI Catalysts can form vinyl-terminated low molecular weight polyethylenes, ultra-high molecular weight amorphous ethylene-propylene copolymers and atactic polypropylenes, highly isotactic and syndiotactic polypropylenes with exceptionally high peak melting temperatures, well-defined and controlled multimodal polyethylenes, and high molecular weight regio-irregular poly(higher alpha-olefin)s. In addition, FI Catalysts combined with MgCl(2)-based compounds can produce polymers that exhibit desirable morphological features (e.g., very high bulk density polyethylenes and highly controlled particle-size polyethylenes) that are difficult to obtain with conventionally supported catalysts. In addition, FI Catalysts are capable of creating a large variety of living-polymerization-based polymers, including terminally functionalized polymers and block copolymers from ethylene, propylene, and higher alpha-olefins. Furthermore, some of the FI Catalysts can furnish living-polymerization-based polymers catalytically by combination with appropriate chain transfer agents. Therefore, the development of FI Catalysts has enabled some crucial advances in the fields of polymerization catalysis and polymer syntheses.

A new and effective method for the activation, and simultaneously, immobilization of bis(phenoxyimine) early-transition-metal complexes for olefin polymerization (known as FI catalysts), which makes use of MgCl(2)/R'(n)Al(OR)(3-n) as an activator/support, has been developed. Ti-, Zr-, and V-FI catalysts combined with this MgCl(2)-based compound can form highly active MgCl(2)-supported single-site catalysts capable of demonstrating superior catalytic properties, compared to the corresponding homogeneous methylaluminoxane- (Ti- and Zr-FI catalysts) or alkylaluminum-activation systems (V-FI catalysts), in terms of their catalytic activity, molecular weight, stereoselectivity, and comonomer incorporation. Additionally, these new catalysts can produce polymers of significant morphology with high efficiency. Notably, the MgCl(2)-based compounds can also effectively activate and immobilize the early-to-late transition-metal complexes that have emerged recently. Thus, the application of MgCl(2)-based compounds as activators/supports for transition-metal complexes for olefin polymerization provides a conceptually new strategy for the development of methylaluminoxane- and borate-free, high-performance, single-site catalysts capable of controlling polymer morphology.

A new ethylene polymerization catalyst system containing a phenoxy-imine ligated V complex and a MgCl2-based compound has been discovered. Unlike ordinary V-based catalysts, the system exhibits higher activities at elevated temperatures, and the activity reached a very high value of 65100 kg-PE/mol-cat/h at 75 °C, representing the first example of a highly active, thermally robust V-based ethylene polymerization catalyst system.

MAO-free new single-site catalyst systems have been developed for olefin polymerization, which are comprised of bis(phenoxy-imine) Ti, Zr, or V complexes (Ti–, Zr–, or V–FI Catalysts) and MgCl2-based compounds. These new catalyst combinations are highly active single-site (Ti–FI Catalysts), exceptionally active (Zr–FI Catalysts), or highly active, thermally robust, single-site (V–FI Catalyst) catalysts for ethylene polymerization. The catalysts can display higher catalytic performance (i.e., catalytic activity, stereoselectivity, thermal stability) than those activated by the well-established MAO activators. In addition, these catalysts are supported, and thus possess a technological advantage vis-à-vis control over polymer morphology, which is essential for commercial application. Therefore, the application of MgCl2-based compounds capable of working both as an activator and a support for non-metallocene complexes provides a conceptually new strategy for the development of high-performance supported single-site catalysts.

No abstract