期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 54, 期 16, 页码 4857-4860出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201412052
关键词
EPR spectroscopy; heterogeneous catalysis; polymerization; titanium; Ziegler-Natta catalysts
资金
- Dutch Polymer Institute (DPI) [754]
The typical activation of a fourth generation Ziegler-Natta catalyst TiCl4/MgCl2/phthalate with triethyl aluminum generates Ti(3+)centers that are investigated by multi-frequency continuous wave and pulse EPR methods. Two families of isolated, molecule-like Ti(3+)species have been identified. A comparison of the experimentally derived gtensors and Cl-35,Cl-37 hyperfine and nuclear-quadrupole tensors with DFT-computed values suggests that the dominant EPR-active Ti(3+)species is located on MgCl2(110) surfaces (or equivalent MgCl2 terminations with tetra-coordinated Mg). O-2 reactivity tests show that a fraction of these Tisites is chemically accessible, an important result in view of the search for the true catalyst active site in olefin polymerization.
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