Polyethers as potential electron donors for Ziegler-Natta ethylene polymerization catalysts

Poly(ethylene glycol) (PEG) and poly(tetrahydrofuran) (PTHF) were studied as possible electron donors for heterogeneous Ziegler-Natta catalysts employed for ethylene polymerization. Two synthetic routes were applied for the preparation of the catalysts by mixing the polyether and TiCl4 with delta-MgCl2 support in the same step or at different stages of the catalyst synthesis. The Fourier transform infrared spectroscopy (FT-IR) studies revealed a clear interaction between PEG and delta-MgCl2 inducing changes in the chain conformation of the polyether. If PEG was added at the same stage with TiCl4, a yellow PEG/TiCl4 complex was formed and the activity of the catalyst was decreased. A partial decomposition of PTHF to tetrahydrofuran (THF) in contact with delta-MgCl2 was evidenced from the FT-IR and nuclear magnetic resonance spectroscopy data. The decomposition could be induced by the Lewis acid sites or by possible organomagnesium compounds present in the synthesized delta-MgCl2. However, the decomposition did not have a negative effect on the polymerization behavior of the prepared catalysts, when compared to the reference catalysts where THF was initially used as a donor. The catalysts prepared with polyethers as electron donor showed good activity in ethylene (around 1000 kgP/mol(Ti) h) and in ethylene/1-hexene (around 1600 kgP/mol(Ti) h) polymerizations. (C) 2014 Elsevier B.V. All rights reserved.