TY - JOUR A1 - Kricheldorf, H.R. A1 - Eggerstedt, S. A1 - Krüger, Ralph-Peter T1 - Macrocycles, 6a / MALDI-TOF mass spectrometry of tin-initiated macrocyclic polylactones in comparison to classical mass-spectroscopic methods PY - 1999 SN - 1022-1352 SN - 1521-3935 VL - 200 IS - 6 SP - 1284 EP - 1291 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-2166 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Hauser, K. A1 - Krüger, Ralph-Peter A1 - Schulz, Günter T1 - Macrocycles 12. Ring-Opening Polycondensations of Tin-Containing Macrocycles with Bis(Thioarylester)s N2 - 2,2-Dibutyl-2-stanna-1,3-dioxepane (DSDOP) was polycondensed with bis(4-chlorothiophenyl) suberat under various reaction conditions, but only moderate molecular weights (Mn 10000) were obtained. The MALDI-TOF mass spectrosmetry revealed the formation of cyclic oligo- and polyesters in addition to linear species having OH, CO2H, and unreacted 4-chlorothiophenyl ester endgroups. Furthermore, -Caprolactone (-CL) was polymerized with DSDOP as the initiator at monomer/initiator (M/I) ratios of 20 and 50. The resulting tin-containing macrocyclic polylactones were reacted with sebacic acid bis(4-thiocresyl)ester at three different temperatures and with different reaction times. Analogous polycondensations were conducted with suberic acid bis(4-chlorothiophenyl) ester. The presence of thioarylester endgroups in the isolated polyesters was checked by 1H NMR spectroscopy. The highest conversions were found at long reaction times (24 or 72 hours), or after the addition of pyridine and N,N-dimethylaminopyridine as catalysts. Despite high conversions, the number average molecular weights (Mn's) did not exceed values around 20000. Even in the samples having the highest molecular weights, unreacted 4-chlorothiophenylester endgroups were detected by GPC measurements evaluated with a UV-detector. It is concluded that both factors, cyclization and incomplete conversion, contribute to the limitation of the chain growth. KW - Ring-Opening Polycondensations KW - Macrocycles KW - Polyesters PY - 2000 DO - https://doi.org/10.1081/MA-100101099 SN - 1060-1325 SN - 1520-5738 VL - 37 IS - 4 SP - 379 EP - 394 PB - Taylor & Francis CY - Philadelphia, PA AN - OPUS4-2167 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Probst, N. A1 - Schwarz, G. A1 - Schulz, Günter A1 - Krüger, Ralph-Peter T1 - New Polymer Syntheses - 107. Aliphatic Poly(thio ester)s by Ring-Opening Polycondensation of 2-Stanna-1,3-Dithiacycloalkanes N2 - We prepared 2,2-dibutyl-2-stanna-1,3-dithiacycloalkanes from dibutyltin oxide and ,-dimercaptoalkanes. Heterocycles with five-, six-, seven-, or nine-ring members were used as bifunctional monomers for polycondensations with aliphatic dicarboxylic acid chlorides. These polycondensations conducted in bulk were highly exothermic and yielded poly(thio ester)s with number average molecular weights (Mn's) in the range of 5000-30,000 Da. These poly(thio ester)s proved to be rapidly crystallizing materials with melting temperatures in the range of 90-150 °C. In addition to the success of the new synthetic approach, two interesting and unpredictable results were obtained. All volatile species detectable by matrix assisted laser desorption induced-time of flight (MALDI-TOF) mass spectrometry were cyclic oligo- and poly(thio ester)s. Second, several polyesters showed a reversible first-order change of the crystal modification as identified by differential scanning calorimetry measurements and X-ray scattering with variation of the temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3656-3664, 2000 KW - Poly(thio-ester)s KW - Ring-opening polycondensation KW - Macrocycles KW - Change of crystal structure PY - 2000 DO - https://doi.org/10.1002/1099-0518(20001001)38:19<3656::AID-POLA190>3.0.CO;2-M SN - 0360-6376 SN - 0887-624X VL - 38 IS - 19 SP - 3656 EP - 3664 PB - Wiley CY - Hoboken, NJ AN - OPUS4-2170 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Reuther, F. A1 - Krüger, Ralph-Peter A1 - Schulz, Günter A1 - Baehr, G. A1 - Westerwelle, U. A1 - Gruetzner, G. ED - Houlihan, F. M. T1 - Tailored novolak resins for advanced photoresists by a two-step procedure - new insight into the molecular structure by coupling GPC and MALDI-TOF-MS T2 - 17th Annual SPIE Conference on Advances in Resist Technology and Processing CY - Santa Clara, CA, USA DA - 2000-02-28 KW - Novolak KW - Structure KW - Synthesis KW - Gel permeation KW - Chromatography KW - MALDI-TOF-MS PY - 2000 SN - 0-8194-3617-8 SN - 1605-7422 N1 - Serientitel: SPIE proceedings series – Series title: SPIE proceedings series IS - 3999 SP - 464 EP - 471 PB - SPIE CY - Bellingham AN - OPUS4-2171 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter T1 - Characterization of unusual Silsesquioxane-Based Polymer Architectures Based on the Coupling of Liquid Chromatography and MALDI-TOF-MS T2 - XIth International Symposium on Organosilicon Chemistry CY - Montpellier, France DA - 1996-09-01 PY - 1996 AN - OPUS4-3416 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter T1 - Characterization of thermal and hydrolytic degradation of polylactides by Liquid Chromatography and MALDI-TOF mass spectrometry T2 - International Symposium on "Biodegradable Materials" and Hamburger Makromolekulares Symposium 1996 CY - Hamburg, Germany DA - 1996-10-07 PY - 1996 AN - OPUS4-3417 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter T1 - Characterization of Polymer Heterogeneity During Degradation Processes by Liquid Chromatography and MALDI-TOF-MS T2 - 9th International Symposium on Polymer Analysis and Characterization CY - Oxford, England DA - 1996-07-01 PY - 1996 AN - OPUS4-3453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter T1 - Characterization of Polyesters and Copolyesters by Coupled Liquid Chromatographic and Spectroscopic Techniques T2 - 11. Internationale Fachtagung Polymerwerkstoffe 2004 CY - Halle (Saale), Germany DA - 2004-09-29 PY - 2004 AN - OPUS4-4339 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter T1 - Structure and Related Properties of Polymerizable Silsesquioxanes as a Matrix for Dental Composites T2 - 13th International Workshop on Sol-Gel Science and Technology CY - Los Angeles, CA, USA DA - 2005-08-21 PY - 2005 AN - OPUS4-10748 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter T1 - Determination of functionality and molar mass distribution of aliphatic polyesters by orthogonal liquid chromatography, Part I: Off-line investigation of poly-(1,6-hexanediol adipates) PY - 1994 SN - 0148-3919 VL - 17 SP - 3069 EP - 3090 PB - Dekker CY - New York, NY AN - OPUS4-2139 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter T1 - New Results of Determination of Polymer Heterogeneity by Two-Dimensional Orthogonal Liquid Chromatography T2 - International GPC Symposium CY - Lake Buena Vista, FL, USA DA - 1994-06-05 PY - 1994 SP - 273 EP - 275 PB - Gordon and Breach CY - St. Helier, Jersey AN - OPUS4-2140 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Spickermann, J. A1 - Martin, K. A1 - Räder, H.J. A1 - Müllen, K. A1 - Schlaad, H. A1 - Müller, A. H. E. A1 - Krüger, Ralph-Peter T1 - Quantitative analysis of broad molecular weight distributions obtained by MALDI-TOF mass spectrometry PY - 1996 SN - 1469-0667 SN - 1356-1049 SN - 1365-0718 IS - 2 SP - 161 EP - 165 PB - IM Publications CY - Chichester AN - OPUS4-2153 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wachsen, O. A1 - Reichert, K.H. A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter T1 - Thermal decomposition of biodegradable polyesters - III. Studies on the mechanisms of thermal degradation of oligo-L-lactide using SEC, LACCC and MALDI-TOF-MS PY - 1997 SN - 0141-3910 SN - 1873-2321 VL - 55 SP - 225 EP - 231 PB - Applied Science Publ. CY - London AN - OPUS4-2154 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tressl, R. A1 - Wondrak, G. T. A1 - Krüger, Ralph-Peter A1 - Rewicki, D. T1 - New Melanoidin-like Maillard Polymers from 2-Deoxypentoses KW - Maillard system 2-deoxy-D-ribose / methylamine KW - Oligomerization of N-methyl-2-hydroxymethyl(and hydroxyl[13C]methyl)pyrrole KW - Antioxidative activity KW - Model compounds for melanoidins PY - 1998 SN - 0021-8561 SN - 1520-5118 VL - 46 IS - 1 SP - 104 EP - 110 PB - American Chemical Society CY - Columbus, Ohio AN - OPUS4-2158 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 - GEN A1 - Tressl, R. A1 - Wondrak, G. T. A1 - Kersten, E. A1 - Krüger, Ralph-Peter A1 - Rewicki, D. ED - Shibamoto, T. ED - Terao, J. ED - Osawa, T. T1 - Identification of maillard type polymers with antioxidative activity T2 - 213th National Meeting of the American Chemical Society CY - San Francisco, CA, USA DA - 1997-04-13 PY - 1998 SN - 0-8412-3573-2 SN - 0097-6156 N1 - Serientitel: ACS Symposium Series – Series title: ACS Symposium Series IS - 702 SP - 209 EP - 220 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2160 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Tressl, R. A1 - Kersten, E. A1 - Wondrak, G. T. A1 - Rewicki, D. A1 - Krüger, Ralph-Peter ED - O'Brien, J. T1 - Fragmentation of Sugar Skeletons and Formation of Maillard Polymers T2 - 6th International Symposium on the Maillard Reaction CY - London, England, UK DA - 1997-07-27 PY - 1998 SN - 0-85404-733-6 SN - 0260-6291 N1 - Serientitel: Special publication / Royal Society of Chemistry – Series title: Special publication / Royal Society of Chemistry IS - 223 SP - 69 EP - 75 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-2161 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Veith, M. A1 - Elsässer, R. A1 - Krüger, Ralph-Peter T1 - Synthesis of Dendrimers with a N-Si-C Framework N2 - A novel family of air-stable dendrimers with a N-Si-C framework has been prepared up to the fourth generation. The divergent synthesis starts with the hydrosilylation of the trisilazane N(SiMe2vinyl)3 [0-G(vinyl)] by HSiMe2Cl, which gives the three-directional core molecule N(SiMe2CH2CH2SiMe2Cl)3 [0-G(Cl)]. A 1-to-2 branching achieved by reacting the core molecule [0-G(Cl)] with 3 equiv of KN(SiMe2vinyl)2 affords the first generation dendrimer [1-G(vinyl)]. By repeating the above two steps, the second [2-G(vinyl)], third [3-G(vinyl)], and fourth generation [4-G(vinyl)] can be obtained. The compounds have been characterized by 1H, 13C, and 29Si NMR spectroscopy, by elemental analysis, and up to the third generation by MALDI-TOF mass spectrometry. Gel permeation chromatography was used to prove the fourth generation [4-G(vinyl)]. PY - 1999 DO - https://doi.org/10.1021/om9807708 SN - 0276-7333 SN - 1520-6041 VL - 18 IS - 4 SP - 656 EP - 661 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2162 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter T1 - Determination of polymer heterogeneity by two-dimensional orthogonal liquid chromatography KW - Orthogonal chromatography KW - Size exclusion chromatography KW - Liquid adsorption chromatography at critical conditions KW - Matrix-assisted laser desorption ionization time-of-flight mass spectrometry KW - Polyester KW - Polyether PY - 1996 SN - 1023-666X SN - 1563-5341 VL - 2 SP - 221 EP - 235 PB - Gordon and Breach Publ. CY - Amsterdam AN - OPUS4-2146 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sonnenschein, H. A1 - Kreher, T. A1 - Gründemann, E. A1 - Krüger, Ralph-Peter A1 - Kunath, A. A1 - Zabel, V. T1 - Novel Redox-Active Cyclophanes Based on 3,3'-Bisindolizines - Synthesis and Chirality PY - 1996 SN - 0022-3263 SN - 1520-6904 VL - 61 SP - 710 EP - 714 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2147 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Leukel, J. A1 - Burchard, W. A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter T1 - Mechanism of the anionic copolymerization of anhydride- cured epoxies-analysisted by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) PY - 1996 SN - 1022-1336 SN - 1521-3927 VL - 17 SP - 359 EP - 366 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-2148 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter A1 - Wachsen, O. T1 - New aspects of determination of polymer heterogeneity by 2-dimensional orthogonal liquid chromatography and MALDI-TOF-MS PY - 1996 SN - 1022-1360 SN - 0258-0322 SN - 1521-3900 VL - 110 SP - 155 EP - 176 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-2150 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gähde, J. A1 - Mix, Renate A1 - Krüger, Ralph-Peter A1 - Goering, Harald A1 - Funke, W. A1 - Hermann, U. T1 - Adherence of Liquid Crystalline TDI-Polyurethanes to Steel KW - Main-chain liquid crystalline polyurethanes KW - Primer on steel KW - Pull-off test KW - Wet adhesion of alkyd melamine resin KW - Mesogenic unit KW - Glass transition temperature KW - Hard segments KW - Soft segments PY - 1996 SN - 0021-8464 SN - 1545-5823 VL - 58 SP - 243 EP - 251 PB - Gordon & Breach CY - New York, NY AN - OPUS4-2152 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 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 - TY - CONF A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter T1 - Polymer Characterization by Two-Dimensional HPLC and MALDI-TOF-MS T2 - 7th International Symposium on Polymer Analysis and Characterization (ISPAC) CY - Les Diablerets, Switzerland DA - 1994-05-24 PY - 1994 PB - Gordon and Breach CY - St. Helier, Jersey AN - OPUS4-2196 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sonnenschein, Helmut A1 - Kreher, Th. A1 - Krüger, Ralph-Peter A1 - Ahlers, B. T1 - Synthesis of brigded indolizines-starting materials for molecular tweezers T2 - XVI th European Colloquium on Heterocyclic Chemistry CY - Bled, Slovenia DA - 1994-09-25 PY - 1994 CY - Bled, Slovenia AN - OPUS4-2198 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Paulus, G. A1 - Resch, M. A1 - Schulz, Günter ED - Darms, R. ED - Suter, U. T1 - Polymer Characterization by MALDI-TOF-MS and Combination with HPLC T2 - 5th European Polymer Federation Symposium on Polymeric Materials (EPF) CY - Basel, Switzerland DA - 1994-10-09 PY - 1994 SN - 3-85739-297-5 SN - 0258-0322 VL - 5 PB - Hüthig & Wepf CY - Zug AN - OPUS4-2200 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Kilz, P. A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter ED - Provder, T. T1 - Two-dimensional chromatography for the deformulation of complex copolymers PY - 1995 SN - 0-8412-3132-X N1 - Serientitel: Advances in chemistry series – Series title: Advances in chemistry series IS - 247 SP - 223 EP - 241 PB - American Chemical Society CY - Washington AN - OPUS4-2185 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Just, Ulrich A1 - Krüger, Ralph-Peter ED - Auner, N. T1 - Investigations of Chemical Heterogeneity in Polydimethylsiloxanes using SFC, HPLC and MALDI-MS T2 - 2. Münchner Silicontage ; 2nd Munich Silicon Days CY - Munich, Germany DA - 1994-01-01 PY - 1996 SN - 3-527-29254-3 SP - 625 EP - 632 PB - VCH CY - Weinheim AN - OPUS4-2186 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter A1 - Rikowski, E. ED - Auner, N. T1 - Synthesis of Polyhedral Hexa-, Octa-, Deca- and Dodeca-Silsesquioxanes, Separation by NP-HPLC, SEC and LAC, Characterization by MALDI-TOF-MS KW - Silsesquioxanes KW - NP-HPLC KW - LAC KW - SEC KW - MALDI-TOF-MS PY - 2000 SN - 3-527-29854-1 SP - 545 ff. PB - Wiley-VCH CY - Weinheim AN - OPUS4-2187 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Much, Helmut A1 - Krüger, Ralph-Peter A1 - Schulz, Günter T1 - Investigation of Macromer Heterogeneity by Two-Dimensional HPLC and MALDI-TOF-MS T2 - 19th International Symposium on Column Liquid Chromatography CY - Innsbruck, Austria DA - 1995-05-28 PY - 1995 CY - Innsbruck AN - OPUS4-2204 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maier, B. A1 - Trathnigg, B. A1 - Much, Helmut A1 - Krüger, Ralph-Peter A1 - Berek, D. T1 - Characterization of polyethers using different chromatographic techniques and MALDI-TOF-MS PY - 1995 CY - Innsbruck AN - OPUS4-2205 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter T1 - Investigation of Macromer Heterogeneity by 2D-HPLC and MALDI-TOF-MS T2 - Präsentationsveranstaltung des Instituts für Angewandte Chemie Berlin-Adlershof e.V. CY - Berlin, Germany DA - 1995-09-26 PY - 1995 CY - Berlin AN - OPUS4-2207 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 - Krüger, Ralph-Peter T1 - Cyclic Hyperbranched Poly(ether ketone)s Derived from 3,5-Bis(4-fluorobenzoyl)phenol N2 - 3,5-Bis(4-fluorobenzoyl)phenol was polycondensed under various reaction conditions. Low molecular weights were obtained (Mn < 8000 Da), and MALDI-TOF mass spectrometry indicated that the chain growth was limited by cyclization. In the best mass spectra the cyclic, hyperbranched poly(ether ketone)s were detectable up to masses around 14 000 Da. When 4,4'-difluordiphenyl sulfone was added, star-shaped polymers having a diphenyl sulfone star center were formed, but cyclization was not completely suppressed. The results were compared to those obtained from "linear polycondensations" based on 4,4'-difluorobenzophenone (DFBP) and 4-tert-butylcatechol or bisphenol A. The poly(ether ketone)s of DFBP had also low molecular weights and contained high fractions of cycles. It is concluded that also in the case of hyperbranched polymers cyclization competes with propagation at any stage of the polycondensation at any concentration. Therefore, the fundamental trend of any "abn" polycondensation is the formation of star-shaped polymers having a cyclic core and hyperbranched star arms. PY - 2003 DO - https://doi.org/10.1021/ma021799x SN - 0024-9297 SN - 1520-5835 VL - 36 SP - 5551 EP - 5558 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2622 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 - CONF A1 - Krüger, Ralph-Peter T1 - Characterization of Silicon-Polymers by Liquid Chromatography and MALDI-TOF-MS T2 - GDCh-Hauptversammlung in Verbindung mit dem 37. IUPAC Congress CY - Berlin, Germany DA - 1999-08-14 PY - 1999 AN - OPUS4-3547 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Krüger, Ralph-Peter T1 - Book review: H. Pasch and W. Schrepp "MALDI-TOF Mass Spectrometry of Synthetic Polymers" PY - 2004 DO - https://doi.org/10.1002/macp.200400155 SN - 1022-1352 SN - 1521-3935 VL - 205 SP - 1284 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-3567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Shaik, A.-A. A1 - Richter, M. A1 - Kricheldorf, H. A1 - Krüger, Ralph-Peter T1 - New polymer syntheses - CIX. Biodegradable, alternating copolyesters of terephthalic acid, aliphatic dicarboxylic acids, and alkane diols N2 - Copolyesters with an alternating sequence of terephthalic acid and aliphatic dicarboxylic acids were prepared with three different methods. First, dicarboxylic acid dichlorides were reacted with bis(2-hydroxyethyl)terephthalate (BHET) in refluxing 1,2-dichlorobenzene. Second, the same monomers were polycondensed at 0-20 °C in the presence of pyridine. Third, dicarboxylic acid dichlorides and silylated BHET were polycondensed in bulk. Only this third method gave satisfactory molecular weights. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed that the copolyesters prepared by the pyridine and silyl methods might have contained considerable fractions of cyclic oligoesters and polyesters despite the absence of transesterification and backbiting processes. The alternating sequences and thermal properties were characterized with 1H NMR spectroscopy and differential scanning calorimetry measurements, respectively. In agreement with the alternating sequence, all copolyesters proved to be crystalline, but the crystallization was extremely slow [slower than that of poly(ethylene terephthalate)]. A second series of alternating copolyesters was prepared by the polycondensation of silylated bis(4-hydroxybut- yl)terephthalate with various aliphatic dicarboxylic acid dichlorides. The resulting copolyesters showed significantly higher rates of crystallization, and the melting temperatures were higher than those of the BHET-based copolyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3371-3382, 2001 KW - Poly(ethylene terephthalate) KW - Poly(butylene terephthalate) KW - Alternating sequence KW - Macrocycles KW - Crystallization KW - Biodegradable polyesters PY - 2001 DO - https://doi.org/10.1002/pola.1320 SN - 0360-6376 SN - 0887-624X VL - 39 IS - 19 SP - 3371 EP - 3382 PB - Wiley CY - Hoboken, NJ AN - OPUS4-2173 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bünger, H. A1 - Krüger, Ralph-Peter A1 - Pietschmann, S. A1 - Wüstneck, N. A1 - Kaufner, L. A1 - Tschiersch, R. A1 - Pison, U. T1 - Two hydrophobic protein fractions of ovine pulmonary surfactant: Isolation, characterisation and biophysical activity N2 - Pulmonary surfactant contains two extremely hydrophobic proteins, SP-B and SP-C. We present a novel HPLC method for the preparation of these hydrophobic proteins. It is based on size-exclusion chromatography using the apolar stationary-phase butyl silica gel and isocratic elution with acidified chloroform/methanol. Samples for HPLC were prepared from sheep lung lavage fluid by centrifugation and extraction with chloroform/methanol. Amino acid analyses of the two protein fractions revealed sequences that are consistent with SP-B and SP-C, respectively. MALDI-TOF-MS analyses of the SP-B fraction showed one major peak of dimeric SP-B with m/z 17,361, and additional peaks of monomeric and oligomeric forms, which are predominantly even numbered. The SP-C fraction showed a peak at m/z 4200, consistent with the theoretical mass of the dipalmitoylated form of this protein. The biophysical activity of pure sheep SP-B and SP-C was evaluated by measuring the surface tension using axisymmetric drop shape analysis for captive bubbles. We found distinct surface pressure versus surface area isotherms of SP-B and SP-C indicating different biophysical activities for these surfactant proteins. The new preparative HPLC method is able to replace the established, time-consuming low-pressure liquid chromatography method for the isolation of SP-B and SP-C from lipids. KW - Surfactant proteins KW - SP-B KW - SP-C KW - Preparative HPLC KW - MALDI-TOF-MS KW - Surface pressure KW - Captive bubble PY - 2001 DO - https://doi.org/10.1006/prep.2001.1510 SN - 1046-5928 SN - 1096-0279 VL - 23 IS - 2 SP - 319 EP - 327 PB - Elsevier CY - Amsterdam AN - OPUS4-2174 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Czichocki, G. A1 - Heger, R. A1 - Much, Helmut A1 - Krüger, Ralph-Peter A1 - Goedel, W.A. T1 - Synthesis of Polyisoprenes with Sulfonate Head Groups and their Purification by HPLC PY - 2001 SN - 0932-3414 SN - 0040-3490 VL - 38 IS - 3 SP - 168 EP - 172 PB - Hanser CY - München AN - OPUS4-2175 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Böhme, S. A1 - Schwarz, G. A1 - Krüger, Ralph-Peter A1 - Schulz, Günter T1 - Macrocycles 18. The Role of Cyclization in Syntheses of Poly(ether-sulfone)s N2 - Poly(ether-sulfone)s having an identical backbone were prepared by four different methods. First, silylated bisphenol A (BSBA) was polycondensed with 4,4'-difluorodiphenyl sulfone (DFDPS) and K2CO3 in N-methylpyrrolidone with variation of the temperature. Second, analogous polycondensation were conducted using CsF as catalyst (and no K2CO3). Third, CsF-catalyzed polycondensations BSBA and DFDPS were conducted in bulk up to 290 C. Fourth, free bisphenol was polycondensed with DFDPS or 4,4'-dichlorodiphenyl sulfone and K2CO3 in DMSO with azeotropic removal of water. MALDI-TOF mass spectroscopy revealed that the first method mainly yielded cyclic poly(ether-sulfone)s which were detected up to masses around 13 000 Da. These and other results suggest that these polycondensations take a kinetically kontrolled course at tempeatures 145 C. This interpretation is also valid for the fourth method where high yields of cycles were obtained with DFDPS. With the less reactive 4,4'-dichlorodiphenyl sulfone lower conversions, lower molecular weights and lower fractions of cycles were found. In contrast to KF (resulting from K2CO3) CsF cleaves the poly(ether sulfone) backbone at temperatures > 145 C. Smaller amounts of smaller cycles were found in these CsF-catalyzed polycondensations which were in this case the result of thermodynamically controlled "back-biting degradation". PY - 2001 DO - https://doi.org/10.1021/ma010218l SN - 0024-9297 SN - 1520-5835 VL - 34 SP - 8886 EP - 8893 PB - American Chemical Society CY - Washington, DC AN - OPUS4-2176 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Rabenstein, M. A1 - Langanke, D. A1 - Schwarz, G. A1 - Schmidt, M. A1 - Maskos, M. A1 - Krüger, Ralph-Peter T1 - Ring-closing polycondensations N2 - The role of cyclization in polycondensations is discussed for two different scenarios: thermodynamically-controlled polycondensation (TCPs) on the one hand and kinetically-controlled polycondensations (KCPs) on the other. The classical Carothers–Flory theory of step-growth polymerization does not include cyclization reactions. However, TCPs involve the formation of cycles via ‘back-biting degradation’, and when the ring–chain equilibrium is on the side of the cycles the main reaction products of the TCP will be cyclic oligomers. Two groups of examples are discussed: polycondensations of salicyclic acid derivatives (e.g. aspirin) and polycondensations of dibutyltin derivatives with long {alpha}-, {omega}-diols or dicarboxylic acids. Furthermore, various kinetically-controlled syntheses of polyesters and polyamides were studied and carefully optimized in the direction of high molecular weights. High fractions of cyclic oligomers and polymers were found by MALDI-TOF mass spectrometry, and their fractions increased with optimization of the process for molecular weight. These results disagree with the Carothers–Flory theory but agree with the theoretical background of the Ruggli–Ziegler dilution method (RZDM). When poly(ether-sulfone)s were prepared from 4,4'-difluorodiphenylsulfone and silylated bisphenol-A two different scenarios were found. With CsF as catalyst at a temperature of more than 145°C cyclic oligoethers were formed under thermodynamic control. When the polycondensation was promoted with K2CO3 in N-methylpyrolidone at ?145°C the formation of cyclic oligoethers and polyethers occurred under kinetic control. A new mathematical formula is presented correlating the average degree of polymerization with the conversion and taking into account the competition between cyclization and propagation. PY - 2001 DO - https://doi.org/10.1088/0954-0083/13/2/312 SN - 0954-0083 SN - 1361-6412 VL - 13 SP - S123 EP - S136 PB - Sage Publ. CY - London AN - OPUS4-2178 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 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 - 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 - CONF A1 - Grimm, B. A1 - Krüger, Ralph-Peter A1 - Schrader, S. A1 - Prescher, D. T1 - Molecular structure investigations on fluorine-containing polyazomethines by means of MALDI-TOF-MS technique T2 - Berliner Polymerentage 2000 CY - Berlin, Germany DA - 2000-10-09 PY - 2000 CY - Berlin AN - OPUS4-2253 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schlaad, H. A1 - Müller, A. A1 - Spickermann, J. A1 - Räder, H. A1 - Krüger, Ralph-Peter T1 - Quantitative Analysis of Molecular Weight Distribution Obtained by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF-MS) T2 - 2nd International Conference on Molecular Mass Characterization of Synthetic and Natural Polymers CY - Bradford, England, UK DA - 1996-04-01 PY - 1996 CY - Bradford AN - OPUS4-2218 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Krüger, Ralph-Peter A1 - Much, Helmut A1 - Schulz, Günter A1 - Frey, H. T1 - Characterization of unusual Silsesquioxane-Based Polymer Architectures Based on the Coupling of Liquid Chromatography and MALDI-TOF-MS T2 - 11th International Symposium on Organosilicon Chemistry CY - Montpellier, France DA - 1996-09-01 PY - 1996 CY - Montpellier AN - OPUS4-2222 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Prescher, D. A1 - Grimm, B. A1 - Krüger, Ralph-Peter A1 - Schrader, S. T1 - To the formation of F-containing polyazomethines - investigation of the reaction products by MALDI TOF mass spectrometry T2 - 16th International Symposium Fluorine Chemistry CY - Durham, England, UK DA - 2000-07-16 PY - 2000 AN - OPUS4-2246 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Bünger, H. A1 - Pison, U. A1 - Krüger, Ralph-Peter ED - Yeung, E. T1 - Separation of hydrophobic pulmonary surfactant proteins using preparative HPLC with UV detection T2 - 24th International Symposium on High Performance Liquid Phase Separations and Related Techniques ; 24th HPLC 2000 CY - Seattle, WA, USA DA - 2000-06-24 PY - 2000 SN - 0021-9673 PB - Elsevier CY - Amsterdam AN - OPUS4-2249 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Müller, A. A1 - Krüger, Ralph-Peter T1 - Quantitative analysis of molecular weight distribution obtained by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry T2 - DECHEMA-Diskussionstagung "Neue Methoden der Polymeranalytik" CY - Mainz, Germany DA - 1996-10-07 PY - 1996 CY - Mainz AN - OPUS4-2224 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -