A zirconium complex having two phenoxy-imine chelate ligands, bis[N-(3-tert-butylsalicylidene)anilinato]zirconium(IV)dichloride (1), was found to display a very high ethylene polymerization activity of 550 kg of polymer/mmol of cat‚h with a viscosity average molecular weight (M v ) value of 0.9 × 10 4 at 25 °C at atmospheric pressure using methylalumoxane (MAO) as a cocatalyst. This activity is 1 order of magnitude larger than that exhibited by Cp 2 ZrCl 2 under the same polymerization conditions. The use of Ph 3 CB(C 6 F 5 ) 4 / i-Bu 3 Al in place of MAO as a cocatalyst resulted in extremely high molecular weight polyethylene, M v 505 × 10 4 , with an activity of 11 kg of polymer/mmol of cat‚h at 50 °C. This M v value is one of the highest values displayed by homogeneous olefin polymerization catalysts. Complex 1, using Ph 3 CB(C 6 F 5 ) 4 /i-Bu 3 Al as a cocatalyst, provided a high molecular weight ethylene-propylene copolymer, M v 109 × 10 4 , with 8 kg of polymer/mmol of cat‚h activity at a propylene content of 20.7 mol %. X-ray analysis revealed that complex 1 adopts a distorted octahedral coordination structure around the zirconium metal and that two oxygen atoms are situated in trans position while two nitrogen atoms and two chlorine atoms are situated in cis position. DFT calculations suggest that the active species derived from complex 1 possesses two available cis-located sites for efficient ethylene polymerization. Changing the tert-butyl group in the phenoxy benzene ring enhanced the polymerization activity. Bis[N-(3-cumyl-5-methylsalicylidene)cyclohexylaminato]zirconium(IV)dichloride ( 7) with MAO displayed an ethylene polymerization activity of 4315 kg of polymer/mmol of cat‚h at 25 °C at atmospheric pressure. This activity corresponds to a catalyst turnover frequency (TOF) value of 42 900/s‚ atm. This TOF value is one of the largest not only for olefin polymerization but also for any known catalytic reaction. Ligands with additional steric congestion near the polymerization reaction center gave increased M v values. The maximum M v value, 220 × 10 4 using MAO, was obtained with bis[N-(3,5-dicumylsalicylidene)-2′-isopropylanilinato]zirconium(IV)dichloride (15). Thus, polyethylenes ranging from low to exceptionally high molecular weights can be obtained from these zirconium complexes by changing the ligand structure and the choice of cocatalyst.

Seven titanium complexes bearing fluorine-containing phenoxy-imine chelate ligands, TiCl(2)[eta(2)-1-[C(H)=NR]-2-O-3-(t)Bu-C(6)H(3)](2) [R = 2,3,4,5,6-pentafluorophenyl (1), R = 2,4,6-trifluorophenyl (2), R = 2,6-difluorophenyl (3), R = 2-fluorophenyl (4), R = 3,4,5-trifluorophenyl (5), R = 3,5-difluorophenyl (6), R = 4-fluorophenyl (7)], were synthesized from the lithium salt of the requisite ligand and TiCl(4) in good yields (22%-76%). X-ray analysis revealed that the complexes 1 and 3 adopt a distorted octahedral structure in which the two phenoxy oxygens are situated in the trans-position while the two imine nitrogens and the two chlorine atoms are located cis to one another, the same spatial disposition as that for the corresponding nonfluorinated complex. Although the Ti-O, Ti-N, and Ti-Cl bond distances for complexes 1 and 3 are very similar to those for the nonfluorinated complex, the bond angles between the ligands (e.g., O-Ti-O, N-Ti-N, and Cl-Ti-Cl) and the Ti-N-C-C torsion angles involving the phenyl on the imine nitrogen are different from those for the nonfluorinated complex, as a result of the introduction of fluorine atoms. Complex 1/methylalumoxane (MAO) catalyst system promoted living ethylene polymerization to produce high molecular weight polyethylenes (M(n) > 400 000) with extremely narrow polydispersities (M(w)/M(n) < 1.20). Very high activities (TOF > 20 000 min(-1) atm(-1)) were observed that are comparable to those of Cp(2)ZrCl(2)/MAO at high polymerization temperatures (25, 50 degrees C). Complexes 2-4, which have a fluorine atom adjacent to the imine nitrogen, behaved as living ethylene polymerization catalysts at 50 degrees C, whereas complexes 5-7, possessing no fluorine adjacent to the imine nitrogen, produced polyethylenes having M(w)/M(n) values of ca. 2 with beta-hydrogen transfer as the main termination pathway. These results together with DFT calculations suggested that the presence of a fluorine atom adjacent to the imine nitrogen is a requirement for the high-temperature living polymerization, and the fluorine of the active species for ethylene polymerization interacts with a beta-hydrogen of a polymer chain, resulting in the prevention of beta-hydrogen transfer. This catalyst system was used for the synthesis of a number of unique block copolymers such as polyethylene-b-poly(ethylene-co-propylene) diblock copolymer and polyethylene-b-poly(ethylene-co-propylene)-b-syndiotactic polypropylene triblock copolymer from ethylene and propylene.

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.

The propylene polymerization behavior of a series of Ti complexes featuring fluorine-containing phenoxy-imine chelate ligands is reported. The Ti complexes combined with methylalumoxane (MAO) can be catalysts for living and, at the same time, stereospecific polymerization of propylene at room temperature or above. DFT calculations suggest that the attractive interaction between a fluorine ortho to the imine nitrogen and a beta-hydrogen of a growing polymer chain is responsible for the achievement of room-temperature living propylene polymerization. Although the Ti complexes possess C(2) symmetry, they are capable of producing highly syndiotactic polypropylenes. (13)C NMR is used to demonstrate that the syndiotacticity is governed by a chain-end control mechanism and that the polymerization is initiated exclusively via 1,2-insertion followed by 2,1-insertion as the principal mode of polymerization. (13)C NMR spectroscopy also elucidated that the polypropylenes produced with the Ti complexes possess regio-block structures. Substitutions on the phenoxy-imine ligands have profound effects on catalytic behavior of the Ti complexes. The steric bulk of the substituent ortho to the phenoxy oxygen plays a decisive role in achieving high syndioselectivity for the chain-end controlled polymerization. Over a temperature range of 0-50 degrees C, Ti complex having a trimethylsilyl group ortho to the phenoxy oxygen forms highly syndiotactic, nearly monodisperse polypropylenes (94-90% rr) with extremely high peak melting temperatures (T(m) = 156-149 degrees C). The polymerization behavior of the Ti complexes can be explained well by the recently proposed site-inversion mechanism for the formation of syndiotactic polypropylene by a Ti complex having a pair of fluorine-containing phenoxy-imine ligands.

Bis(pyrrolide-imine) Ti complexes in conjunction with methylalumoxane (MAO) were found to work as efficient catalysts for the copolymerization of ethylene and norbornene to afford unique copolymers via an addition-type polymerization mechanism. The catalysts exhibited very high norbornene incorporation, superior to that obtained with Me(2)Si(Me(4)Cp)(N-tert-Bu)TiCl(2) (CGC). The sterically open and highly electrophilic nature of the catalysts is probably responsible for the excellent norbornene incorporation. The catalysts displayed a marked tendency to produce alternating copolymers, which have stereoirregular structures despite the C(2) symmetric nature of the catalysts. The norbornene/ethylene molar ratio in the polymerization medium had a profound influence on the molecular weight distribution of the resulting copolymer. At norbornene/ethylene ratios larger than ca. 1, the catalysts mediated room-temperature living copolymerization of ethylene and norbornene to form high molecular weight monodisperse copolymers (M(n) > 500,000, M(w)/M(n) < 1.20). (13)C NMR spectroscopic analysis of a copolymer, produced under conditions that gave low molecular weight, demonstrated that the copolymerization is initiated by norbornene insertion and that the catalyst mostly exists as a norbornene-last-inserted species under living conditions. Polymerization behavior coupled with DFT calculations suggested that the highly controlled living polymerization stems from the fact that the catalysts possess high affinity and high incorporation ability for norbornene as well as the characteristics of a living ethylene polymerization though under limited conditions (M(n) 225,000, M(w)/M(n) 1.15, 10-s polymerization, 25 degrees C). With the catalyst, unique block copolymers [i.e., poly(ethylene-co-norbornene)(1)-b-poly(ethylene-co-norbornene)(2), PE-b-poly(ethylene-co-norbornene)] were successfully synthesized from ethylene and norbornene. Transmission electron microscopy (TEM) indicated that the PE-b-poly(ethylene-co-norbornene) possesses high potential as a new material consisting of crystalline and amorphous segments which are chemically linked.