Synthesis of Zr (IV), Hf (IV) complexes of butanesulphonylhydrazones as the new post-metallocene catalysts and investigation of their catalyst activities in olefin polymerization

In this work, butane sulfonic acide hydrazide (L1) and its derivatives; salicylaldehydebutanesulfonylhydrazone (L2), 5methylsalicylaldehyde butane sulfonylhydrazone (L3), 5Cl-salicylaldehydebutanesulfonylhydrazone (L4), 2-hydroxyacetophenonebutanesulfonylhydrazone (L5), 5-methyl-2-hydroxy acetophenonebutanesulfonylhydrazone (L6) and 5-Cl-2-hydroxyacetophenone butanesulfonylhydrazone (L7) compounds were synthesized. The structures of new aromatic butane sulfonylhydrazone derivatives were investigated by using FT-IR, 1H-NMR, 13C-NMR and ESI-MS, spectrophotometric method. Structure of salicylaldehydebutanesulfonylhydrazone (L2) and 5-Cl-2-hydroxyaceto phenone butanesulfonyl hydrazone (L7) compounds were also supported by single crystal X-ray diffraction method. A single deprotonated and two deprotonated sodium salts (NaHL and Na2 L, L = L2-L7) of aromatic butane sulfonylhydrazones (H2L) were synthesized and characterized by using FT-IR, 13C-NMR and 1H-NMR spectroscopic techniques. The Zr (IV) and Hf (IV) metal complexes were synthesized with obtained 12 butanesulfonylhydrazone sodium salts and their structures were investigated byusing FT-IR, 1H-NMR, MALDI-TOF MS spectroscopic methods and conductivity measurements. Catalytic Activities of some complexes were investigated for olefin polymerization. Ethylene was used for polimerization process and polyethylene was obtained as product. The structure of polyethylene was investigated by using spectrophotometric ATR-IR methods and differential scanning calorimetry (DSC) measurements. DSC measurements show that the product is generally high-density polyetylene (HDPE).Key Words : Hydrazide, aromatic butanesulfonyl hydrazone, Zr (IV), Hf (IV) complexes, X ray diffraction method, post- metallocene catalysts, olefin polymerization