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Citation: LIU Sanrong, LIU Jingyu, LI Yuesheng. Ethylene Polymerization by Monochloro Non-Bridged Half-Metallocene-type Zirconium Complexes Containing Phosphine Oxide-(thio) phenolate Chelating Ligands as Catalyst at High Temperature[J]. Chinese Journal of Applied Chemistry, ;2013, 30(11): 1293-1298. doi: 10.3724/SP.J.1095.2013.30198 shu

Ethylene Polymerization by Monochloro Non-Bridged Half-Metallocene-type Zirconium Complexes Containing Phosphine Oxide-(thio) phenolate Chelating Ligands as Catalyst at High Temperature

a. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;
b. University of Chinese Academy of Sciences, Beijing 100049, China

Received Date: 23 April 2013
Revised Date: 7 June 2013

Ethylene polymerizations were explored by monochloro half-zirconocene complexes containing phosphine oxide-(thio) phenolate chelating ligands of the type,ClCp'Zr[X-2-R¹-4-R²-6-(PH₂P=O)C₆H₂]₂(Cp'=C₅H₅,a:X=O,R¹=Ph,R²=H;b:X=O,R¹=F,R²=H;c:X=O,R¹=^tBu,R²=H;d:X=O,R¹=R²=^tBu;e:X=O,R¹=SiMe₃,R²=H;f:X=S,R¹=SiMe₃,R²=H;Cp'=C₅Me₅;g:X=O,R¹=SiMe₃,R²=H) in the presence of Ph₃CB(C₆F₅)₄/ⁱBu₃Al as co-catalyst at high temperature(50~125℃). As reveled by the polymerization results,under optimized reaction temperature of 75℃,complexes a~d were efficient ethylene polymerization catalysts under high temperature(50~100℃). Catalytic activity was improved by increasing the steric bulk of R¹ substituent or the introduction of electron withdrawing groups at the same position. The occurrence of trimethylsilyl rendered a greatly improved temperature resistance for catalyst e than those of catalysts a~d,exhibiting an ethylene polymerization activity of 5628 kg/(mol Zr·h) under 100℃ optimized reaction temperature. The variation of coordinated atom or the substituents at the Cp moiety had certain influences upon the catalytic activity and the PDI of the resulting polymer material.
- monochloro half-metallocene-type zirconium complexes,
- ethylene polymerization,
- high temperature and high activity
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