Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium Complex
A series of new fluorenylamido-ligated zirconium complexes bearing an electron-donating adamantyl group on the amido ligand were synthesized and characterized by elemental analysis, 1H NMR, and single crystal X-ray analysis. The coordination mode of the fluorenyl ligand to the zirconium metal was η3...
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doaj-ce5bb5a34cf04524a363b2eadcead28f2020-11-24T20:49:02ZengMDPI AGPolymers2073-43602017-11-0191163210.3390/polym9110632polym9110632Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium ComplexYanjie Sun0Shuhui Li1Takeshi Shiono2Zhengguo Cai3State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, ChinaState Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, ChinaGraduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, JapanState Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, ChinaA series of new fluorenylamido-ligated zirconium complexes bearing an electron-donating adamantyl group on the amido ligand were synthesized and characterized by elemental analysis, 1H NMR, and single crystal X-ray analysis. The coordination mode of the fluorenyl ligand to the zirconium metal was η3 manner, and all the complexes were Cs-symmetric in solution. The complexes showed moderate activity (1.0 × 105 g-polymer mol-Zr−1·h−1), even at a low Al/Zr ratio of 50. The increase of propylene pressure improved the activity by one order of magnitude (up to 1.0 × 106 g-polymer mol-Ti−1·h−1). All catalyst systems gave syndiotactic polypropylene, where the complex containing the 3,6-di-t-butyl fluorenyl ligand was more effective for the enhancement of the syndiospecificity. The increase of propylene pressure also improved the syndiospecificity with the syndiotactic pentad of 0.96 and the melting point of 159 °C.https://www.mdpi.com/2073-4360/9/11/632constrained geometry catalystszirconium complexadamantyl substituentpropylene polymerizationsyndiospecificity |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Yanjie Sun Shuhui Li Takeshi Shiono Zhengguo Cai |
spellingShingle |
Yanjie Sun Shuhui Li Takeshi Shiono Zhengguo Cai Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium Complex Polymers constrained geometry catalysts zirconium complex adamantyl substituent propylene polymerization syndiospecificity |
author_facet |
Yanjie Sun Shuhui Li Takeshi Shiono Zhengguo Cai |
author_sort |
Yanjie Sun |
title |
Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium Complex |
title_short |
Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium Complex |
title_full |
Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium Complex |
title_fullStr |
Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium Complex |
title_full_unstemmed |
Substituent Effects of Adamantyl Group on Amido Ligand in Syndiospecific Polymerization of Propylene with Ansa-Dimethylsilylene(Fluorenyl)(Amido) Zirconium Complex |
title_sort |
substituent effects of adamantyl group on amido ligand in syndiospecific polymerization of propylene with ansa-dimethylsilylene(fluorenyl)(amido) zirconium complex |
publisher |
MDPI AG |
series |
Polymers |
issn |
2073-4360 |
publishDate |
2017-11-01 |
description |
A series of new fluorenylamido-ligated zirconium complexes bearing an electron-donating adamantyl group on the amido ligand were synthesized and characterized by elemental analysis, 1H NMR, and single crystal X-ray analysis. The coordination mode of the fluorenyl ligand to the zirconium metal was η3 manner, and all the complexes were Cs-symmetric in solution. The complexes showed moderate activity (1.0 × 105 g-polymer mol-Zr−1·h−1), even at a low Al/Zr ratio of 50. The increase of propylene pressure improved the activity by one order of magnitude (up to 1.0 × 106 g-polymer mol-Ti−1·h−1). All catalyst systems gave syndiotactic polypropylene, where the complex containing the 3,6-di-t-butyl fluorenyl ligand was more effective for the enhancement of the syndiospecificity. The increase of propylene pressure also improved the syndiospecificity with the syndiotactic pentad of 0.96 and the melting point of 159 °C. |
topic |
constrained geometry catalysts zirconium complex adamantyl substituent propylene polymerization syndiospecificity |
url |
https://www.mdpi.com/2073-4360/9/11/632 |
work_keys_str_mv |
AT yanjiesun substituenteffectsofadamantylgrouponamidoligandinsyndiospecificpolymerizationofpropylenewithansadimethylsilylenefluorenylamidozirconiumcomplex AT shuhuili substituenteffectsofadamantylgrouponamidoligandinsyndiospecificpolymerizationofpropylenewithansadimethylsilylenefluorenylamidozirconiumcomplex AT takeshishiono substituenteffectsofadamantylgrouponamidoligandinsyndiospecificpolymerizationofpropylenewithansadimethylsilylenefluorenylamidozirconiumcomplex AT zhengguocai substituenteffectsofadamantylgrouponamidoligandinsyndiospecificpolymerizationofpropylenewithansadimethylsilylenefluorenylamidozirconiumcomplex |
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1716807030819258368 |