FI Catalysts: new olefin polymerization catalysts for the creation of value-added polymers

• Published in: Chemical record Vol. 4; no. 3; pp. 137 - 158
• Main Authors: Mitani, Makoto, Saito, Junji, Ishii, Sei-ichi, Nakayama, Yasushi, Makio, Haruyuki, Matsukawa, Naoto, Matsui, Shigekazu, Mohri, Jun-ichi, Furuyama, Rieko, Terao, Hiroshi, Bando, Hideki, Tanaka, Hidetsugu, Fujita, Terunori
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 2004
• Subjects: group 4 transition metal complexes; N, O ligands; O ligands; olefin polymerization; polyolefins
• ISSN: 1527-8999; 1528-0691
• DOI: 10.1002/tcr.20010

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 α‐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 α‐olefin)s. In addition, FI Catalysts combined with MgCl2‐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 α‐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. © 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 4: 137–158; 2004: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20010 Based on a ligand‐oriented catalyst design concept, phenoxy–imine‐ligated early transition metal complex catalysts (known as FI Catalysts) have been developed for olefin polymerization. In combination with appropriate cocatalysts, FI Catalysts can display unprecedented polymerization behavior and form a variety of unique polyolefinic materials that were previously unavailable with Ziegler–Natta catalysts. Therefore, the development of FI Catalysts has had an enormous impact on catalyst chemistry and polymer chemistry.