Ethylene and propylene polymerization behavior of a series of bis(phenoxy–imine)titanium complexes

✍ Scribed by Rieko Furuyama; Junji Saito; Sei-ichi Ishii; Makoto Mitani; Shigekazu Matsui; Yasushi Tohi; Haruyuki Makio; Naoto Matsukawa; Hidetsugu Tanaka; Terunori Fujita

• Publisher: Elsevier Science
• Year: 2003
• Tongue: English
• Weight: 140 KB
• Volume: 200
• Category: Article
• ISSN: 1381-1169
• DOI: 10.1016/s1381-1169(03)00096-7

✦ Synopsis

This contribution reports ethylene and propylene polymerization behavior of a series of Ti complexes bearing a pair of phenoxy-imine chelate ligands. The bis(phenoxy-imine)Ti complexes in conjunction with methylalumoxane (MAO) can be active catalysts for the polymerization of ethylene. Unexpectedly, this C 2 symmetric catalyst produces syndiotactic polypropylene. 13 C NMR spectroscopy has revealed that the syndiotacticity arises from a chain-end control mechanism. Substitutions on the phenoxy-imine ligands have substantial effects on both ethylene and propylene polymerization behavior of the complexes. In particular, the steric bulk of the substituent ortho to the phenoxy-oxygen is fundamental to obtaining high activity and high molecular weight for ethylene polymerization and high syndioselectivity for the chain-end controlled propylene polymerization. The highest ethylene polymerization activity, 3240 kg/mol-cat h, exhibited by a complex having a t-butyl group ortho to the phenoxy-oxygen, represents one of the highest reported to date for Ti-based non-metallocene catalysts. Additionally, the polypropylene produced exhibits a T m , 140 • C, and syndioselectivity, rrrr 83.7% (achieved by a complex bearing a trimethylsilyl group ortho to the phenoxy-oxygen) that are among the highest for polypropylenes produced via a chain-end control mechanism. Hence, the bis(phenoxy-imine)Ti complexes are rare examples of non-metallocene catalysts that are useful for the polymerization of not only ethylene but also propylene.