TY - JOUR A1 - Kricheldorf, H. A1 - Chatti, S. A1 - Schwarz, G. A1 - Krüger, Ralph-Peter T1 - Macrocycles 27 - Cyclic Aliphatic Polyesters of Isosorbide N2 - Numerous polycondensations of isosorbide and suberoyl chloride or other aliphatic dicarboxylic acid dichlorides were performed with pyridine as a catalyst and HCl acceptor. The reaction conditions were varied to optimize both the molecular weight and the fraction of cyclic oligo- and polyesters. Furthermore, we attempted to obtain the cyclic monomer by catalyzed back-biting degradation of the molten cyclic polyesters above 220 °C in vacuo. The polyesters were characterized by viscosity and size exclusion chromatographic measurements as well as matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In selected cases, mixtures of linear and cyclic polyesters were treated with a hot solution of partially methylated ß-cyclodextrin in methanol. This treatment allowed for a selective extraction of the linear chains up to approximately 5000 Da. KW - Polycondensation KW - Cyclization KW - Isosorbide KW - Polyesters KW - MALDI PY - 2003 DO - https://doi.org/10.1002/pola.10933 SN - 0360-6376 SN - 0887-624X VL - 41 IS - 21 SP - 3414 EP - 3424 PB - Wiley CY - Hoboken, NJ AN - OPUS4-12017 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Vakhtangishvili, L. A1 - Schwarz, G. A1 - Schulz, Günter A1 - Krüger, Ralph-Peter T1 - Macrocycles 25. Cyclic poly(ether sulfone)s derived from 4-tert-butylcatechol N2 - Poly(ether sulfone)s were prepared by polycondensation of silylated 4-tert-butylcatechol and 4,4?-difluorodiphenylsulfone in N-methylpyrrolidone. The feed ratio and the reaction time were varied to study the influence of stoichiometry and conversion on molecular weight and extent of cyclization. Molecular weights and molecular weight distributions (MWD)s were characterized by SEC measurements calibrated with polystyrene. Light scattering confirmed that calibration with polystyrene gives reasonable results and revealed a tendency towards a bimodal MWD for the samples rich in cycles. The MALDI-TOF mass spectrometry indicated that the extent of cyclization increased with higher conversion and with optimization of the stoichiometry. This interpretation was confirmed by 1H NMR endgroup analyses. For the samples with the highest molar masses only mass peaks of cycles were found, which were detectable up to 20 000 Da before and up to 27 000 Da after fractionation. Via the pseudo-high dilution method low molar mass poly(ether sulfone) containing more than 95 mol% of cycles were prepared, and even these low molar mass samples had broad MWDs. DSC measurements indicated that the glass transition temperatures depend on the structure of the endgroups and increase with higher fractions of cycles. KW - Poly(ether sulfone)s KW - Polycondensation KW - MALDI-TOF mass spectrometry PY - 2003 DO - https://doi.org/10.1016/S0032-3861(03)00410-5 SN - 0032-3861 SN - 1873-2291 VL - 44 SP - 4471 EP - 4480 PB - Springer CY - Berlin AN - OPUS4-2623 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 - Tressl, R. A1 - Wondrak, G. T. A1 - Garbe, L.-A. A1 - Krüger, Ralph-Peter A1 - Rewicki, D. T1 - Pentoses and Hexoses as Sources of New Melanoidin-like Maillard-Polymers KW - Model compounds for melanoidins KW - Pyrroles from pentoses and hexoses KW - Beta-dicarbonyl pathway of the Maillard reaction KW - Polycondensation KW - MALDI-TOF-MS analysis KW - Antioxidative activity of oligomeric model compounds PY - 1998 SN - 0021-8561 SN - 1520-5118 VL - 46 IS - 5 SP - 1765 EP - 1776 PB - American Chemical Society CY - Columbus, Ohio AN - OPUS4-2159 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 -