Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for a-Olefin Polymerization

Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4(M=Ti,Zr) with the corresponding Schiff-base ligand in 1:1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine N,S,N] ligand and TiCl4 in toluene at 120℃. All complexes are well charac-terized by ^1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex If (R^1=CH3,R^2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.

Syntheses of some new group 4 non‐Cp complexes bearing schiff‐base,thiophene diamide ligands respectively and their catalytic activities for α‐olefin polymerization

Totally sixteen new titanium and zirconium non‐Cp complexes supported by Schiff‐base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OP_T‐i)₄ (M=Ti, Zr) with the corresponding Schiff‐base ligand in 1: 1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine N,S,N] ligand and TiCl₄ in toluene at 120 °C. All complexes are well characterized by ¹H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex 1f (R¹=CH₃, R²=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.