Abstract
A multitechnique approach (comprising in situ Fourier transform infrared, diffuse reflectance ultraviolet–visible, and advanced electron paramagnetic resonance spectroscopies, coupled with differential scanning calorimetry analysis) was employed to investigate the local structure and the activation of a heterogeneous ethylene polymerization catalyst obtained by grafting TiCl4 onto a transitional alumina. The activation procedure was found to affect the electronic structure and the coordinative environment of the reduced Ti sites, as well as their interaction with the Al3+ sites, measured in terms of spin density transfer from Ti3+ to nearby Al3+ ions. It was found that the extent of interaction between the two metal sites correlates with the microstructures of the obtained polyethylene. Tuning the synergy between the Ti3+ and Al3+ Lewis acid sites is proposed as an efficient way to modulate the polyethylene microstructure, switching from a high-density polyethylene to a highly branched polyethylene.
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