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
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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.
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