TY - JOUR A1 - Bugel, S. A1 - Hahnel, M. A1 - Kunde, T. A1 - de Sousa Amadeu, Nadar A1 - Sun, Y. A1 - Spieß, A. A1 - Beglau, T. H. Y. A1 - Janiak, C. A1 - Schmidt, B. M. T1 - Synthesis and Characterization of a Crystalline Imine-Based Covalent Organic Framework with Triazine Node and Biphenyl Linker and Its Fluorinated Derivate for CO2/CH4 Separation JF - Materials N2 - A catalyst-free Schiff base reaction was applied to synthesize two imine-linked covalent organic frameworks (COFs). The condensation reaction of 1,3,5-tris-(4-aminophenyl)triazine (TAPT) with 4,4′-biphenyldicarboxaldehyde led to the structure of HHU-COF-1 (HHU = Heinrich-Heine University). The fluorinated analog HHU-COF-2 was obtained with 2,2′,3,3′,5,5′,6,6′-octafluoro-4,4′-biphenyldicarboxaldehyde. Solid-state NMR, infrared spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis confirmed the successful formation of the two network structures. The crystalline materials are characterized by high Brunauer–Emmett–Teller surface areas of 2352 m2/g for HHU-COF-1 and 1356 m2/g for HHU-COF-2. The products of a larger-scale synthesis were applied to prepare mixed-matrix membranes (MMMs) with the polymer Matrimid. CO2/CH4 permeation tests revealed a moderate increase in CO2 permeability at constant selectivity for HHU-COF-1 as a dispersed phase, whereas application of the fluorinated COF led to a CO2/CH4 selectivity increase from 42 for the pure Matrimid membrane to 51 for 8 wt% of HHU-COF-2 and a permeability increase from 6.8 to 13.0 Barrer for the 24 wt% MMM. KW - MOF KW - Filter PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-547632 DO - https://doi.org/10.3390/ma15082807 SN - 1996-1944 VL - 15 IS - 8 SP - 1 EP - 18 PB - MDPI AN - OPUS4-54763 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - 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 JF - Macromolecular chemistry and physics 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 DO - 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 - GEN A1 - Janiak, Ch. A1 - Lange, K.C.H. A1 - Marquardt, P. A1 - Krüger, Ralph-Peter A1 - Hanselmann, R. ED - Sun, J. ED - Janiak, C. T1 - Propene and 1-hexene oligomerization with unbridged alkyl-substituted cyclopentadienyl- and phospholyl-zirconium/MAO catalysts - mechanistic implications from oligomer analyses by NMR, SEC, and MALDI-TOF MS T2 - Advances on organometallic catalysts and olefin polymerization in China and Germany PY - 2001 SP - 117 EP - 142 PB - Chemical Industry Press CY - Bejing AN - OPUS4-2193 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -