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 - TY - JOUR A1 - Kricheldorf, H.R. A1 - Böhme, S. A1 - Krüger, Ralph-Peter T1 - Macrocycles, 16a - Macrocyclic Dibutyltin Dicarboxylates via Thermodynamically Controlled Polycondensations N2 - Various dibutyltin derivatives were polycondensed with aliphatic ,-dicarboxylic acids having chain lengths from 4 (succinic acid) to 22 carbon atoms. White crystalline products were obtained from all experiments, and the structure of the products was independent of the synthetic method. Viscosity measurements revealed low molecular weights (n 1 500 Da) in all cases. Vapor pressure osmometry (VPO) measurements and matrix-assisted laser desorption time-of-flight (MALDI-TOF) mass spectrometry proved that cyclic dimers and trimer were formed from dicarboxylic acids having 6 to 16 carbons, but mainly the monomeric cycle from docosane dioic acid. Heating to 250°C did not change the structure. Therefore, the results indicate that the macrocycles are the result of a thermodynamically controlled ring-closing polycondensation. This means that linear high-molecular weight poly(dibutyltin dicarboxylate)s cannot exist above room temperature. KW - Macrocyclics KW - MALDI KW - Oligomers KW - Polycondensation KW - Thermodynamics PY - 2002 SN - 1022-1352 SN - 1521-3935 VL - 203 IS - 2 SP - 313 EP - 318 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-2181 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Ralph-Peter A1 - Kricheldorf, H.R. A1 - Böhme, S. T1 - Macrocyclic Dibutyltin Dicarboxylates via Thermodynamically Controlled Polycondensations KW - Macrocyclics KW - MALDI KW - Oligomers KW - Polycondensation KW - Thermodynamics PY - 2002 SN - 1022-1352 SN - 1521-3935 IS - 203 SP - 313 EP - 318 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-1656 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Grimm, B. A1 - Krüger, Ralph-Peter A1 - Schrader, S. A1 - Prescher, D. T1 - Molecular structure investigations on fluorine containing polyazomethines by means of the MALDI-TOF-MS technique N2 - Three new aromatic polyazomethines have been synthesized by solution polycondensation reactions of terephthalic dialdehyde with fluorine containing aromatic diamines. The polymers were obtained in high yields. The investigation of these polymers by means of matrix-assisted laser desorption ionization–time-of-flight–mass spectrometry (MALDI–TOF–MS) proved the initial members of the four theoretical possible series of the corresponding oligomers with 2–10 repeating units per molecule. KW - Polyazomethines KW - Oligomers KW - MALDI-TOF-MS PY - 2002 U6 - https://doi.org/10.1016/S0022-1139(01)00498-5 SN - 0022-1139 SN - 1873-3328 VL - 113 SP - 85 EP - 91 PB - Elsevier CY - Amsterdam AN - OPUS4-1657 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -