Fusing Carbocycles of Inequivalent Ring Size to a Bis(imino)pyridine-Iron Ethylene Polymerization Catalyst: Distinctive Effects on Activity, PE Molecular Weight, and Dispersity.

Zheng Wang,Qingbin Liu,Wen-Hua Sun,Yanping Ma,Tongling Liang,Gregory A Solan

doi:10.34133/2019/9426063

Abstract

The 4,6-bis(arylimino)-1,2,3,7,8,9,10-heptahydrocyclohepta[b]quinoline-iron(II) chlorides (aryl = 2,6-Me2C6H3Fe1; 2,6-Et2C6H3Fe2; 2,6-i-Pr2C6H3Fe3; 2,4,6-Me3C6H2Fe4; and 2,6-Et2-4-Me2C6H2Fe5) have been prepared in good yield by a straightforward one-pot reaction of 2,3,7,8,9,10-hexahydro-1H-cyclohepta[b]quinoline-4,6-dione, FeCl2·4H2O, and the appropriate aniline in acetic acid. All ferrous complexes have been characterized by elemental analysis and FT-IR spectroscopy. In addition, the structure of Fe3 has been determined by single crystal X-ray diffraction, which showed the iron center to adopt a distorted square pyramidal geometry with the saturated sections of the fused six- and seven-membered carbocycles to be cis-configured. In combination with either MAO or MMAO, Fe1–Fe5 exhibited exceptionally high activities for ethylene polymerization (up to 15.86 × 106 g(PE) mol−1 (Fe) h−1 at 40°C (MMAO) and 9.60 × 106 g(PE) mol−1 (Fe) h−1 at 60°C (MAO)) and produced highly linear polyethylene (HLPE, Tm ≥ 128°C) with a wide range in molecular weights; in general, the MMAO-promoted polymerizations were more active. Irrespective of the cocatalyst employed, the 2,6-Me2-substituted Fe1 and Fe4 proved the most active while the more sterically hindered 2,6-i-Pr2Fe3 the least but afforded the highest molecular weight polyethylene (Mw: 65.6–72.6 kg mol−1). Multinuclear NMR spectroscopic analysis of the polymer formed using Fe4/MMAO at 40°C showed a preference for fully saturated chain ends with a broad bimodal distribution a feature of the GPC trace (Mw/Mn = 13.4). By contrast, using Fe4/MAO at 60°C a vinyl-terminated polymer of lower molecular weight (Mw = 14.2 kg mol−1) was identified that exhibited a unimodal distribution (Mw/Mn = 3.8). Moreover, the amount of aluminoxane cocatalyst employed, temperature, and run time were also found to be influential on the modality of the polymer.

Highlights

The outstanding productivities attainable by bis(arylimino)pyridine-iron and bis(arylimino)pyridine-cobaltcatalysts (A, Figure 1) for the polymerization of ethylene, initially reported over twenty years ago [1,2,3,4], have spurred a myriad of academic and industrial research disclosures [5,6,7,8,9]
The successful implementation of a 500-ton scale pilot process for the production of linear α-olefins (LAOs) in China that makes use of a 2-imino-1,10-phenanthroline-iron catalyst highlights the enormous potential of this homogeneous technology [6, 8, 20, 21]
The fused ring size has been shown to be pivotal to the catalytic activity and polymeric properties [6, 36,37,38]

Summary

Introduction

The outstanding productivities attainable by bis(arylimino)pyridine-iron and bis(arylimino)pyridine-cobalt (pre)catalysts (A, Figure 1) for the polymerization of ethylene, initially reported over twenty years ago [1,2,3,4], have spurred a myriad of academic and industrial research disclosures [5,6,7,8,9]. As a more recent development, we have demonstrated that cobalt-containing E (Figure 1), incorporating both six- and seven-membered carbocycles, showed the highest catalytic activity of the cobalt-containing A-E series and generated valuable vinyl-terminated PE waxes with narrow molecular weight distributions [38]. Such low molecular weight polymers provide promising raw materials for the production of functional polymers, copolymers, and coating materials [32, 38]

Methods

Results

Conclusion