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Ethylene Copolymerization with 4‑Methylcyclohexene or 1‑Methylcyclopentene by Half-Titanocene Catalysts: Effect of Ligands and Microstructural Analysis of the Copolymers

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journal contribution
posted on 22.01.2018, 12:35 by Hitoshi Harakawa, Srisuda Patamma, Antonella Caterina Boccia, Laura Boggioni, Dino Romano Ferro, Simona Losio, Kotohiro Nomura, Incoronata Tritto
Ethylene copolymerizations with 4-methylcyclohexene (4-MeCHE) or 1-methylcyclopentene (1-MeCPE) have been explored by the aryloxo- or ketimide-modified half-titanocenes, Cp′TiCl2(X) [X: O-2,6-iPr2C6H3; Cp′: 1,2,4-Me3C5H2 (1), tBuC5H4 (2), C5Me5 (Cp*); X: NCtBu2; Cp′: tBuC5H4, Cp, indenyl], linked half-titanocenes, [Me2Si­(C5Me4)­(NR)]­TiCl2 (R = tBu, cyclohexyl), and ordinary metallocenes, [Et­(indenyl)2]­ZrCl2, Cp2ZrCl2, in the presence of methyl­aluminoxane (MAO) cocatalyst. The aryloxo analogues (1, 2) showed rather efficient 4-MeCHE incorporations in a 1,2- (or 2,1-) insertion manner, affording the copolymers with unimodal molecular weight distributions (as well as with uniform compositions observed as single melting temperature by the DSC thermograms), whereas to the others they showed negligible incorporations under the same conditions. Only the 1,2,4-Me3C5H2-aryloxo analogue (1) afforded the copolymers containing 1-MeCPE with uniform compositions, and 1-MeCPE was incorporated with 1,2-insertion as well as after isomerization (1,3-insertion, incorporated as methylene cyclopentane units), whereas incorporation of 1-methyl­cyclohexene (1-MeCHE) was rather negligible.