TY - JOUR A1 - Janiak, Ch. A1 - Lange, K.C.H. A1 - Marquardt, P. A1 - Krüger, Ralph-Peter A1 - Hanselmann, R. T1 - Analyses of Propene and 1-Hexene Oligomers from Zirconocene/MAO Catalysts - Mechanistic Implications by NMR, SEC and MALDI-TOF MS N2 - A series of Cp(C5H5)ZrCl2 and Cp2ZrCl2 pre-catalysts (Cp = C5HMe4, C4Me4P, C5Me5, C5H4tBu, C5H3-1,3-tBu2, C5H2-1,2,4-tBu3) together with (C5H5)2ZrCl2 was used for the directed oligomerization of propene and 1-hexene in comparative experiments. Oligomer characterization was carried out by 1H NMR, SEC (GPC), MALDI-TOF MS, cryoscopy and Raman spectroscopy. From 1H NMR the nature and relative ratio of the double-bond end group is determined together with n if every oligomer molecule contains such a double-bond end group. Normally vinylidene double bonds (from -hydrogen elimination) are found. From 1H NMR and MALDI-TOF MS also vinyl end groups (from -methyl elimination) are observed in the case of oligopropenes with (C4Me4P)- (C5H5)ZrCl2 and with the symmetrical methyl containing Cp2ZrCl2 pre-catalysts. The vinylidene/vinyl ratio depends on the ligand and increases from C5HMe4 (65/35) over C4Me4P (61/39) to C5Me5 (9/91). A comparison of n from 1H NMR and SEC together with MALDI-TOF MS shows that the phospholyl-zirconocenes and (C5HMe4)2ZrCl2 also exhibit chain transfer to aluminium, thereby giving saturated oligomers. KW - Chain transfer KW - MALDI KW - Metallocene catalysts KW - Oligomers KW - Polyolefins PY - 2002 U6 - https://doi.org/10.1002/1521-3935(20020101)203:1<129::AID-MACP129>3.0.CO;2-C SN - 1022-1352 SN - 1521-3935 VL - 203 IS - 1 SP - 129 EP - 138 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-2179 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -