SYNTHESES, CHARACTERIZATION AND ETHYLENE POLYMERIZATION OF HALF-SANDWICH GROUP IV METAL COMPLEXES WITH TRIDENTATE [O,N,S] LIGANDS

Ya-lin Qiao Ping Hu Guo-xin Jin

Citation:  Ya-lin Qiao, Ping Hu, Guo-xin Jin. SYNTHESES, CHARACTERIZATION AND ETHYLENE POLYMERIZATION OF HALF-SANDWICH GROUP IV METAL COMPLEXES WITH TRIDENTATE [O,N,S] LIGANDS[J]. Chinese Journal of Polymer Science, 2013, 31(5): 760-768. doi: 10.1007/s10118-013-1265-0 shu

SYNTHESES, CHARACTERIZATION AND ETHYLENE POLYMERIZATION OF HALF-SANDWICH GROUP IV METAL COMPLEXES WITH TRIDENTATE [O,N,S] LIGANDS

    通讯作者: Guo-xin Jin,
  • 基金项目:

    This work was financially supported by the Shanghai Science and Technology Committee (08DZ2270500, 08DJ1400103), Shanghai Leading Academic Discipline Project (B108) and the National Basic Research Program of China (2009CB825300, 2010DFA41160).

摘要: A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-But4-Me-6-((2-(SC6H5)C6H4N=CHC6H2O)]- (La) and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-But4-Me-6-((2-(SC6H5)C6H4N-CH2C6H2O)]2- (Lb) have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group IV metal complexes CpTi[O-NS]Cl2 (1a), CpZr[O-NS]Cl2 (1b), CpTi[O-N-S]Cl (2a), CpZr[O-N-S]Cl (2b) and Cp*Zr[O-N-S]Cl (2c) were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp*ZrCl3, and characterized by IR, 1H-NMR, 13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane (MAO) as co-catalyst up to 1.58 107 g-PEmol-Zr-1h-1. The good catalytic activities can be maintained even at high temperatures such as 100℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.

English


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  • 发布日期:  2013-05-05
  • 收稿日期:  2012-12-04
  • 修回日期:  2013-01-01
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