TY - JOUR A1 - Chabbah, T. A1 - Chatti, S. A1 - Zouaoui, F. A1 - Jlalia, A. A1 - Gaiji, H. A1 - Abderrazak, H. A1 - Casablanca, H. A1 - Mercier, R. A1 - Weidner, Steffen A1 - Errachid, A. A1 - Marestin, C. A1 - Jaffrezic-Renault, N. T1 - New poly(ether-phosphoramide)s sulfides based on green resources as sensitive films for the specific impedimetric detection of nickel ions N2 - For the development of selective and sensitive chemical sensors, we have developed a new family of poly(etherphosphoramide) polymers. These polymers were obtained with satisfactory yields by nucleophilic aromatic polycondensation using isosorbide as green resources, and bisphenol A with two novel difluoro phosphinothioic amide monomers. Unprecedented, the thiophosphorylated aminoheterocycles monomers, functionalized with two heterocyclic amine, N-methylpiperazine and morpholine were successfully obtained by nucleophilic substitution reaction of P(S)–Cl compound. The resulting polymers were characterized by different analytical techniques (NMR, MALDI–ToF MS, GPC, DSC, and ATG). The resulting partially green polymers, having tertiary phosphine sulfide with P–N side chain functionalities along the main chain of polymers are the sensitive film at the surface of a gold electrode for the impedimetric detection of Cd, Ni, Pb and Hg. The bio-based poly(etherphosphoramide) functionalized with N-methylpiperazine modified sensor showed better analytical performance than petrochemical based polymers for the detection of Ni2+. A detection limit of 50 pM was obtained which is very low compared to the previously published electrochemical sensors for nickel detection. KW - Poly(ether-phosphoramide)s sulfides KW - Green chemistry KW - Polymer film KW - MALDI TOF MS PY - 2022 DO - https://doi.org/10.1016/j.talanta.2022.123550 VL - 247 IS - 123550 SP - 1 EP - 9 PB - Elsevier B.V. AN - OPUS4-54980 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Jlalia, I. A1 - Chabbah, T. A1 - Chatti, S. A1 - Schiets, F. A1 - Casabianca, H. A1 - Marestin, C. A1 - Mercier, R. A1 - Weidner, Steffen A1 - Kricheldorf, H. R. A1 - Errachid, A. A1 - Vulliet, E. A1 - Hammani, M. A1 - Jaffrezic-Renault, N. T1 - Alternating bio-based pyridinic copolymers modified with hydrophilic and hydrophobic spacers as sorbents of aromatic pollutants N2 - The main objective of this work was to design new advanced sorbent phases, alternating copolymers, derived from isosorbide and 2,6-difluorpyridine, to be used for the removal of aromatic organic pollutants present in water at low concentrations. Six different monomers, dianhydrohexitols isomers and bisphenol derivatives, weresynthesized in order to make it possible to study their hydrophilic and hydrophobiceffect on the sorption efficiency of the resulting polymeric phases. Before this study, we have confirmed the chemicals structures, molecular weights, and thermal properties of the obtained polymeric phases. Sorption results show a higher adsorption efficiency of P6 co-poly(ether-pyridine) based on bisphenol substituted with pyridineunits, for all tested pollutants, hydrophobic and hydrophilic ones, due to its less compact structure. Two aromatic organic pollutants, p-hydroxybenzoic acid and toluicacid, were selected as sorbates to study the adsorption characteristic, kinetics and isotherms of the copoly(ether pyridine) P6. Langmuir model led to a better fitting of the sorption isotherms; the sorption of toluic acid is easier than of that p-hydroxybenzoic acid. Comparing 1/n values for benzoic acid was two time lower for P6 compared to that for biochar and for crosslinked methacrylate resin, showing a higher efficiency KW - Alternating co-poly(ether pyridine)s KW - Aromatic organic compounds, KW - Biosourced isosorbide KW - Sorption isotherm KW - Sorption mechanism PY - 2021 DO - https://doi.org/10.1002/pat.5578 VL - 33 IS - 4 SP - 1057 EP - 1068 PB - Wiley Online Library AN - OPUS4-54031 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Brirmi, M A1 - Chabbah, T. A1 - Chatti, S. A1 - Schiets, F. A1 - Casabianca, H. A1 - Marestin, C. A1 - Mercier, R. A1 - Weidner, Steffen A1 - Errachid, A. A1 - Jaffrezic-Renault, N. A1 - Ben Romdhane, H. T1 - Effect of the pendent groups on biobased polymers, obtained from click chemistry suitable, for the adsorption of organic pollutants from water N2 - In this work, four triazole-based poly(ether-pyridine)s polymers were synthesized and used as an adsorbent for the removal of phenolic compounds from aqueous solutions. For this purpose, new fluoromonomers containing 1,2,3-triazole units were prepared by the Cu(I)-catalyzed 1,3-dipolar cycloaddition reaction and then used for the elaboration of novel poly(ether-pyridine-triazole)s (PEPTs) by direct polyconden-sation with isosorbide and bisphenol A. Chemical structure of fluorinated pyridinicmonomers as well as resulting polymers was confirmed by 1H and 19F NMR spectroscopic methods. The thermal behavior of the obtained PEPTs was characterized using differential scanning calorimetry and thermogravimetric analysis. Results of sorption showed that polymers can be effectively used as a sorbent for the removal of polarorganic pollutants. The isosorbide-based poly(ether-pyridine-triazole) which contains hydrophilic hydroxyl groups as pendants chains (P4) exhibited the highest sorption efficiencies (78%–100% after 1 h). In order to explain the results an adsorption mech-anism mainly based on π–π interactions and hydrogen bonding with the pendent groups is proposed. KW - Adsorption KW - Biobased polymers KW - Cycloaddition KW - Pentafluoropyridine KW - Phenolic compounds PY - 2022 DO - https://doi.org/10.1002/pat.5809 SN - 1042-7147 SP - 1 EP - 21 PB - Wiley online library AN - OPUS4-55389 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mechichi, R. A1 - Chabbah, T. A1 - Chatti, S. A1 - Jlalia, I. A1 - Sanglar, Corinne A1 - Casablanca, H. A1 - Vulliet, E. A1 - Marestin, C. A1 - Mercier, R. A1 - Weidner, Steffen A1 - Errachid, A. A1 - Hammani, M. A1 - Jaffrezic-Renault, N. A1 - Abderrazak, H. T1 - Semi‑interpenetrating Network‑Coated Silica Gel Based on Green Resources for the Efcient Adsorption of Aromatic Pollutants from Waters N2 - In the framework of the development of green analytical chemistry, a silica gel (SG) coated with a semi-penetrating network based on the partially biosourced poly(ethersulfone) is studied for a greener extraction process of aromatic organic pollutants. An optimized composition of the semi-penetrating network (80% of the linear polymer (LP): isosorbide-based poly(ethersulfone) and 20% cross-linking agent (XP) type bismaleimide) leads to a total adsorption of the selected aromatic pollutants, whatever their hydrophilicity. Adsorption characteristic, kinetics and isotherms of the SG-semi-INP LP80/XP20 for p-hydroxybenzoic acid and for toluic acid were studied. Langmuir model led to a better ftting of the adsorption isotherms; the adsorption of toluic acid is easier than that of p-hydroxybenzoic acid. 1/n values of benzoic acid was lower for SGsemi-INP LP80/XP20 compared to biochar and to cross-linked methacrylate resin, showing a higher adsorption efciency. KW - Isosorbide KW - Semi-interpenetrating networks KW - Silica gel modification KW - Aromatic pollutants KW - Adsorption PY - 2022 DO - https://doi.org/10.1007/s42250-022-00463 SN - 2522-5758 SP - 1 EP - 18 PB - Springer AN - OPUS4-55720 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lahcini, M. A1 - Qayouh, H. A1 - Yashiro, T. A1 - Weidner, Steffen A1 - Kricheldorf, H.R. T1 - Bismuth-triflate-catalyzed polymerizations of epsilon-caprolactone N2 - εCL was polymerized using the triflates of lanthanum, samarium, magnesium, aluminum, scandium, and bismuth as catalysts. Bismuth triflate proved to be extraordinarily reactive, and catalyzed polymerizations of εCL even at 20 °C. Adding DTBMP reduced the polymerization rate only slightly. Furthermore, no evidence of a cationic mechanism was found by end‐group analyses. Polymerization at 20 °C either in bulk or in solution only yielded polyesters of low or medium molecular weights. Yet addition of alcohols allowed for a proper control of molecular weight and end‐groups. Additionally, low catalyst concentrations and low temperature resulted in narrow molecular weight distributions and polylactones almost free of cyclic compounds. KW - Bismuth KW - Epsilon-caprolactone KW - Ring-opening polymerization KW - Telechelic polyesters PY - 2011 DO - https://doi.org/10.1002/macp.201000517 SN - 1022-1352 SN - 1521-3935 VL - 212 IS - 6 SP - 583 EP - 591 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-23514 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Koshkina, Olga A1 - Lang, Thomas A1 - Thiermann, R. A1 - Docter, D. A1 - Stauber, R.H. A1 - Secker, C. A1 - Schlaad, H. A1 - Weidner, Steffen A1 - Mohr, B. A1 - Maskos, M. A1 - Bertin, Annabelle T1 - Temperature-triggered protein adsorption on polymer-coated nanoparticles in serum N2 - The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle’s physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 µm. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanoparticles and proteins and the accumulation of nanoparticles in a targeted body region. PY - 2015 DO - https://doi.org/10.1021/acs.langmuir.5b00537 SN - 0743-7463 SN - 1520-5827 VL - 31 IS - 32 SP - 8873 EP - 8881 PB - American Chemical Society CY - Washington, DC AN - OPUS4-34163 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Cortez, L. A1 - Squirrel, A. A1 - Boley, N. A1 - Garcia, C. A1 - van Berkel, P.M. A1 - Boisson, G. A1 - Foster, H. A1 - Papadakis, I. A1 - Steffen, Bernd T1 - How to interpret information from proficiency test exercises concerning the relative performance of accredited laboratories N2 - If the results from various proficiency tests are used to compare the performance of accredited and non-accredited laboratories, great care must be taken not to come to contradicting conclusions when interpreting them. This paper intends to draw the attention to various aspects that should be taken into account when trying to make conclusions from the relative performance of accredited laboratories in proficiency testing. KW - Proficiency test exercises KW - Accredited laboratories KW - Relative performance PY - 2003 DO - https://doi.org/10.1007/s00769-003-0674-0 SN - 0949-1775 SN - 1432-0517 VL - 8 IS - 11 SP - 511 EP - 513 PB - Springer CY - Berlin AN - OPUS4-1843 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Czichocki, G. A1 - Fiedler, H. A1 - Haage, K. A1 - Much, Helmut A1 - Weidner, Steffen T1 - Characterization of alkyl polyglycosides by both reversed-phase and normal-phase modes of high-performance liquid chromatography N2 - Alkyl polyglycosides today represent the most important sugar surfactant. Nonionic sugar surfactants produced via different synthetic routes are mixtures of alkyl homologues, oligomers, anomers and isomers. Alkyl homologues and oligomers of alkyl mono- and diglucosides were separated by reversed-phase high-performance liquid chromatography (HPLC) with methanol–water as the mobile phase using a gradient elution. The gradient was optimized in respect to a simultaneous separation of alkyl glycosides according to their alkyl chain length and alkyl polyoxyethylene glucosides with regard to their length of the polyoxyethylene spacer. The separation of alkyl glycosides into ?- and ?-anomers was carried out by normal-phase HPLC with isooctane–ethyl acetate (60:40, v/v)–2-propanol in the gradient mode. Light scattering detection was used. Matrix-assisted laser desorption ionization time-of-flight mass spectra of alkyl glucosides and dodecyl glucosides with oxyethylene spacer groups are presented. PY - 2002 DO - https://doi.org/10.1016/S0021-9673(01)01459-5 SN - 0021-9673 VL - 943 IS - 2 SP - 241 EP - 250 PB - Elsevier CY - Amsterdam AN - OPUS4-11099 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mühlhan, C. A1 - Weidner, Steffen A1 - Friedrich, Jörg Florian A1 - Nowack, H. T1 - Improvement of bonding properties of polypropylene by low-pressure plasma treatment PY - 1999 SN - 0257-8972 VL - 116-119 SP - 783 EP - 787 PB - Elsevier Science CY - Lausanne AN - OPUS4-6982 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhao, J. A1 - Schlaad, H. A1 - Weidner, Steffen A1 - Antonietti, M. T1 - Synthesis of terpene-poly(ethylene oxide)s by t-BuP4-promoted anionic ring-opening polymerization N2 - Terpene alcohols (menthol, retinol, cholesterol, and betulin) together with the phosphazene base t-BuP4 were used as initiating systems for anionic ring-opening polymerization of ethylene oxide. The polymerizations were conducted in a controlled manner with the initial molar ratio of t-BuP4 to hydroxyl groups of 0.01–0.2, yielding a series of biohybrid polymers comprising terpene entities and poly(ethylene oxide) (PEO) chains with low polydispersities and tunable compositions (57–87 wt% of PEO). Samples were characterized by NMR and UV/visible spectroscopy, MALDI-TOF mass spectrometry, and size exclusion chromatography; thermal properties were studied by differential scanning calorimetry. The concept of this study opens a new toolbox of terpene-based biohybrid polymers with variable properties and functions. KW - ROMP KW - MALDI KW - Amphiphilic polymers KW - Polyethylene oxide PY - 2012 DO - https://doi.org/10.1039/c1py00388g SN - 1759-9954 SN - 1759-9962 VL - 3 IS - 7 SP - 1763 EP - 1768 AN - OPUS4-26026 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Robinson, J.W. A1 - Secker, C. A1 - Weidner, Steffen A1 - Schlaad, H. T1 - Thermoresponsive poly(N-C3 glycine)s N2 - Ring-opening polymerization of N-substituted glycine N-carboxyanhydrides (NCAs) was applied to prepare a series of well-defined poly(N-C3 glycine)s (C3 = n-propyl, allyl, propargyl, and isopropyl), polypeptoids, with molecular weights in the range of 1.8–6.6 kg mol–1. Poly(N-isopropyl glycine), a previously unreported polypeptoid, could be obtained by bulk polymerization of the corresponding NCA in the melt. The samples were characterized by spectroscopy (NMR and FT-IR), size exclusion chromatography (SEC), and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI–ToF MS). The polymers could be dispersed in water up to 20–40 g L–1; the poly(N-propargyl glycine) was not soluble in water. Turbidity measurements of the three water-soluble polypeptoids illustrated cloud point temperatures dependent on structural and electronic properties of the side chain. The cloud point temperatures were found to increase in the order C3 = n-propyl (15–25 °C) < allyl (27–54 °C) < isopropyl (47–58 °C). Long-term annealing of the aqueous solution of poly(N-{n-propyl} glycine) and poly(N-allyl glycine) above the cloud point temperature resulted in the formation of crystalline microparticles with melting points of 188–198 and 157–165 °C (differential scanning calorimetry, DSC), respectively, and rose bud type morphology (scanning electron microscopy, SEM). PY - 2013 DO - https://doi.org/10.1021/ma302412v SN - 0024-9297 SN - 1520-5835 VL - 46 IS - 3 SP - 580 EP - 587 PB - American Chemical Society CY - Washington, DC AN - OPUS4-27696 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Appelhans, Dietmar A1 - Oertel, U. A1 - Mazzeo, R. A1 - Komber, H. A1 - Hoffmann, J. A1 - Weidner, Steffen A1 - Brutschy, B. A1 - Voit, B. A1 - Ottaviani, M.F. T1 - Dense-shell glycodendrimers: UV/Vis and electron paramagnetic resonance study of metal ion complexation N2 - The development of dendritic metal ion carrier systems for use in a biological environment is a challenging task as the carrier system must possess multiple features (e.g. a protective shell for metal decomplexation, targeting functions, metal-intradendrimer complexes, etc.) to substitute for the function of metal proteins in processes such as copper metabolism. Thus, Cu(II) complexation by a series of poly(propyleneimine) glycodendrimers ranging up to the fifth generation that have either a dense maltose or maltotriose shell was investigated by UV/Vis spectroscopy and electron paramagnetic resonance (EPR). As a necessary step towards potential biological application, we elucidated the complexation capacity, location of the Cu(II)-dendrimer complexes and the Cu(II) coordination sphere in the dendritic environment. A generation-dependent Cu(II) complexation was found. Furthermore, analysis of the EPR spectra revealed that internal and external Cu(II) coordination and the symmetry (axial and rhombic) of the generated complexes depend on the oligosaccharide shell, dendrimer generation and the relative concentrations of Cu(II) and the dendrimers. Both axial and rhombic symmetries are generation dependent, but also distort with increasing generation number. External coordination of Cu(II) is supported by sugar groups and water molecules. Finally, a third-generation dendrimer with a maltose shell was used to explore the general complexation behaviour of the dendritic poly(propyleneimine) scaffold towards different metal ions [Cu(II), Ag(I), VO(IV), Ni(II), Eu(III) and UO2(VI)]. KW - Glycodendrimers KW - Metal ion complexation KW - Metal ion-intradendrimer complexes KW - Electron paramagnetic resonance study PY - 2010 DO - https://doi.org/10.1098/rspa.2009.0107 SN - 1364-5021 SN - 0962-8444 SN - 0080-4630 SN - 0950-1207 SN - 1471-2946 VL - 466 SP - 1489 EP - 1513 CY - London, UK AN - OPUS4-21622 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gross, Thomas A1 - Pippig, F. A1 - Merz, B. A1 - Merz, R. A1 - Vohrer, U. A1 - Mix, Renate A1 - Steffen, H. A1 - Bremser, Wolfram A1 - Unger, Wolfgang T1 - Determination of OH groups at plasma oxidised poly(propylene) by TFAA chemical derivatisation XPS: an inter-laboratory comparison N2 - A first inter-laboratory comparison was conducted to demonstrate and document the capability of interested laboratories to measure the fraction of C—OH species on a plasma oxidised poly(propylene) sample by using a chemical derivatisation XPS approach. This report presents the results from that inter-laboratory comparison and includes the data received for the measured values and their associated standard deviations of laboratory means, at a 95% confidence level. The measurements were guided by a protocol developed within the group before and summarised shortly in the paper. Standard deviations that may characterise the state-of-the-art for the nominally simple and rather often practised case of TFAA chemical derivatisation XPS of C—OH species on a plasma oxidised polyolefin surface are calculated following ISO 5725-2:1994. The main conclusion is that the associated degree of equivalence reached by the participating laboratories in this comparison is still low. Further research to improve chemical derivatisation XPS protocols is mandatory. KW - Chemical derivatisation KW - ESCA/XPS KW - Inter-laboratory comparison KW - Photoelectron spectroscopy (PES) KW - Poly(propylene) (PP) PY - 2010 DO - https://doi.org/10.1002/ppap.200900142 SN - 1612-8850 SN - 1612-8869 VL - 7 IS - 6 SP - 494 EP - 503 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-21678 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Kricheldorf, H. R. T1 - Sn(II)2-ethylhexanoate-catalyzed polymerizations of L-lactide in solution – Solution grown crystals of cyclic Poly(L-Lactide)s N2 - L-lactide (LA) was polymerized in toluene by means of neat tin(II) 2-ethylhexanoate (SnOct2). Concentration, time and temperature were varied. The isothermally crystallized polyLAs (PLA) were characterized in the virgin state with regard to topology, molar mass, melting temperature (Tm), crystal modification, high or low Tm morphology, crystallinity and crystal thickness. Even a small amount of solvent favored cyclization relative to polymerization in bulk, so that cyclic polylactides were obtained at 115 ◦C and even at 95 ◦C. At all temperatures the α-modification of PLA was obtained along with crystallinities up to 90%. With 6 M solution the high Tm morphology with Tm’s > 190 ◦C was obtained at 115 ◦C. The crystal thickness of crystallites grown from solution at 115 ◦C was on the average 10–20% higher than that of PLA polymerized in bulk. At a polymerization temperature of 75 ◦C cyclization was incomplete and fewer perfect crystallites were formed. A new hypothesis for the crystal growth of cyclic polyLAs is proposed. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity KW - Polymerization PY - 2022 DO - https://doi.org/10.1016/j.polymer.2022.125142 SN - 0032-3861 VL - 255 SP - 1 EP - 9 PB - Elsevier CY - Oxford AN - OPUS4-55283 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Meyer, A. T1 - Ring-expansion polymerization (REP) of L-lactide with cyclic tin catalysts – About formation of extended ring crystals and optimization of Tm and ΔHm N2 - L-Lactide was polymerized in bulk at 140 °C with three different cyclic tin catalysts and the time was varied from 1 d up to 14 d. The MALDI TOF spectra confirmed the formation of cyclic polylactides (PLAs) and displayed a characteristic change of peak intensity distribution with formation of a “saw tooth pattern”. This pattern confirms a previous hypothesis that cyclic PLAs tend to form crystallites with extended ring conformation and relatively smooth surface. This type of crystallites is formed under thermodynamic control by transesterification on the surface of the crystallites. In this way PLAs with extraordinarily high melting temperatures (Tm's up to 200.6 °C) and extraordinarily high melting enthalpy were obtained (ΔHm's up to 105 J g−1). These ΔHm values require a revision of the maximum ΔHm value calculated in the literature for ideal PLA crystals. KW - Polylactide KW - MALDI-TOF MS KW - ring-expansion polymerization PY - 2022 DO - https://doi.org/10.1016/j.polymer.2022.125516 SN - 0032-3861 VL - 263 SP - 125516 PB - Elsevier Ltd. AN - OPUS4-56338 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Meyer, A. T1 - About the Influence of (Non-)Solvents on the Ring Expansion Polymerization of l-Lactide and the Formation of Extended Ring Crystals N2 - Ring-expansion polymerizations (REPs) catalyzed by two cyclic tin catalysts(2-stanna-1.3-dioxa-4,5,6,7-dibenzazepine [SnBiph] and 2,2-dibutyl-2-stanna-1,3-dithiolane [DSTL) are performed at 140 °C in bulk. Small amounts (4 vol%) of chlorobenzene or other solvents are added to facilitate transesterification reactions (ring–ring equilibration) in the solid poly(l-lactide)s. In the mass range up to m/z 13 000 crystalline PLAs displaying a so-called saw-tooth pattern in the MALDI-TOF mass spectra are obtained indicating the formation of extended-ring crystals. The characteristics of extended-ring crystallites and folded-ring crystallites are discussed. Furthermore, extremely high melting temperatures (Tm’s up to 201.2 °C) and melting enthalpies (𝚫Hm’s up to 106 J g−1)) are found confirming that 𝚫Hmmax, the 𝚫Hm of a perfect crystal, is around or above 115 J g−1 in contrast to literature data. KW - Polylactide KW - MALDI-TOF MS KW - Ring-expansion polymerization KW - Crystals PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565038 DO - https://doi.org/10.1002/macp.202200385 SN - 1022-1352 SP - 1 EP - 8 PB - Wiley VHC-Verlag AN - OPUS4-56503 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - Synthesis of polylactides by means of tin catalysts N2 - This article reviews the usefulness of tin(II) and tin(IV) salts and compounds as catalysts for the polymerization of lactides. The text is subdivided into nine parts mainly reflecting different polymerization strategies, such as ring-opening polymerization (ROP), ring-expansion polymerization (REP), ROP combined with simultaneous polycondensation (ROPPOC), various catalysts with unknown polymerization mechanisms, and polycondensation of lactic acid. Since the toxicity of tin salts and compounds is a matter of concern and frequently mentioned in numerous publications, the first section deals with facts instead of myths about the toxicity of tin salts and compounds. KW - Polylactide KW - MALDI-TOF MS KW - Tin catalysts PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545050 DO - https://doi.org/10.1039/d2py00092j SP - 1 EP - 30 PB - Royal Society for Chemistry AN - OPUS4-54505 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Ring-Expansion Polymerization of 𝝐-Caprolactone, Glycolide, and l-lactide with a Spirocyclic Tin(IV) Catalyst Derived from or 2,2′-Dihydroxy-1,1′-Binaphthyl – New Results and a Revision N2 - In contrast to other cyclic tin bisphenoxides, polymerizations of glycolide and l-lactide with the spirocyclic tin(IV) bis-1,1′-bisnapthoxide yield linear chains having a 1,1′-bisnapthol end group and no cycles. In the case of l-lactide, LA/Cat ratio and temperature are varied and at 160 °C or below, all polylactides mainly consist of even-numbered chains. A total predominance of even-numbered chains is also found for homopolymerization of glycolide, or the copolymerization of glycolide and l-lactide, when conducted <120 °C. Linear chains having a bisnaphthol end group are again the main reaction products of ring-expansion polymerizations (REP) of 𝝐-caprolactone, but above 150 °C cycles are also formed. KW - Polylactide KW - MALDI-TOF MS KW - Polymerization PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-541931 DO - https://doi.org/10.1002/macp.202100308 VL - 222 IS - 24 SP - 1 EP - 10 PB - Wiley VCH GmbH AN - OPUS4-54193 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Falkenhagen, Jana T1 - The role of transesterifications in reversible polycondensations and a reinvestigation of the Jacobson-Beckmann-Stockmayer experiments N2 - The polycondensations of adipic acid and 1,10-decanediol catalyzed by toluene sulfonic acid (TSA) were reinvestigated using MALDI TOF mass spectrometry and NMR spectroscopy. Unexpected reactions of TSA were detected along with incomplete conversion of the monomers. Furthermore, transesterification reactions of end-capped poly(1,10-decanediol adipate) and end-capped poly(ε-caprolactone) catalyzed by TSA were studied. Despite the quite different (ionic) reaction mechanisms, it was found that for polycondensations performed in bulk intermolecular transesterification is more efficient than the intramolecular “back-biting”; this scenario was not considered in the Jacobson–Stockmayer theory of reversible polycondensations. These results also confirm that the Jacobson–Stockmayer explanation of reversible polycondensations solely on the basis of ring chain equilibration is not only devoid of any experimental evidence, but also in contradiction to the results elaborated in this work. KW - Polylactide KW - MALDI-TOF MS KW - Polycondensation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543402 DO - https://doi.org/10.1039/d1py01679b SN - 1759-9962 SP - 1 EP - 9 PB - RSC Publ. CY - Cambridge AN - OPUS4-54340 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - SnOct2-catalyzed and alcohol-initiated ROPS of L-lactide - Control of the molecular weight and the role of cyclization N2 - Ring-opening polymerizations (ROP) of l-lactide (LA) are conducted in bulk at 130, 160, or 180 °C and are initiated with two different alcohols at 160 °C. The lactide/initiator ratio (LA/In) is varied from 50/1 (20/1 at 180 °C) to 900/1 and the lactide/catalyst ratio (LA/Cat) between 2000/1 and 8000/1. At all temperatures a nearly perfect control of number average molecular weight (Mn) via the LA/In ratio is feasible up to LA/In = 200/1, but at higher ratios the Mn value lags behind the theoretical values and the discrepancy increases with higher LA/Cat ratios. Variation of the LA/Cat ratio influences the formation of cycles but does not significantly influence Mn, when the LA/In ratio is kept constant. The formation of cycles is favored by lower In/Cat ratios and is the main reason for the unsatisfactory control of Mn at high LA/In ratios. The results also suggest that the cycles are mainly or exclusively formed by end-to-end cyclization and not, as believed previously, by back-biting. KW - Polylactide KW - MALDI-TOF MS KW - Cyclization KW - Ring-opening polymerization PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543066 DO - https://doi.org/10.1002/macp.202100464 SN - 1521-3935 SP - 1 EP - 10 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54306 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Meyer, A. T1 - Poly(L-lactide): Optimization of Melting Temperature and Melting Enthalpy N2 - Twice recrystallized L-lactide was polymerized with a dozen of different tin or bismuth catalysts in bulk at 160°C for 24 h and was annealed at 150°C afterwards. In two cases Tm values above 197.0°C were obtained. The parameters causing a scattering of the DSC data were studied and discussed. The samples prepared with SnCl2, 2,2-dibutyl-2-stanna-1,3-ditholane (DSTL) or cyclic tin(II) bisphenyldioxide (SnBiph) were subject to annealing programs with variation of time and temperatures, revealing that the Tm´s did not increase. However, an increase of Hm was achieved with maximum values in the range of 93-96 J g-1 corresponding to crystallinities off around 90%. Further studies were performed with once recrystallized L-lactide. Again, those samples directly crystallized from the polymerization process showed the highest Tm values. These data were compared with the equilibrium Tm0 and Hm0 data calculated by several research groups for perfect crystallites. A Tm0 of 213+/-2°C and a Hm0 of 106 J g-1 show the best agreement with the experimental data. The consequences of annealing for the thickness growth of crystallites are discussed on the basis of SAXS measurements. Finally, a comparison of cyclic and linear poly L-lactide)s is discussed. KW - Polylactide KW - MALDI-TOF MS KW - Transesterification PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-538656 DO - https://doi.org/10.1039/D1MA00957E SP - 1 EP - 10 PB - Royal Society for Chemistry AN - OPUS4-53865 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, H. R. T1 - SnOct2-catalyzed ROPs of L-lactide initiated by acidic OH- compounds: Switching from ROP to polycondensation and cyclization N2 - Ring-opening polymerizations (ROPs) of L-lactide are performed in bulk at 130°C with tin(II) 2-ethylhexanoate as catalyst and various phenols of differentacidity as initiators. Crystalline polylactides having phenyl ester end groups are isolated, which are almost free of cyclics. The dispersities and molecular weights are higher than those obtained from alcohol-initiated ROPs under identical conditions. Polymerizations at 160°C yield higher molecular weights than expected from the monomer/initiator ratio and a considerable fraction of cycles. The fraction of cycles increases with higher reactivity of the ester end group indicating that the cycles are formed by end-to-end cyclization. KW - Polylactide KW - MALDI-TOF MS KW - Polymerization PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-540250 DO - https://doi.org/10.1002/pol.20210823 SN - 2642-4150 VL - 60 IS - 5 SP - 785 EP - 793 PB - Wiley AN - OPUS4-54025 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Falkenhagen, Jana T1 - Reversible Polycondensations outside the Jacobson-Stockmayer Theory and a New Concept of Reversible Polycondensations N2 - L-Lactide was polymerized with tin(II)acetate, tin(II)2-ethyl hexanoate, diphenyltin dichloride and dibutyltin bis(pentafluorophenoxide) at 130 °C in bulk. When an alcohol was added as initiator, linear chains free of cycles were formed having a degree of polymerization (DP) according to the lactide/initiator (LA/In) ratio. Analogous polymerizations in the absence of an initiator yielded high molar mass cyclic polylactides. Quite similar results were obtained when ε-caprolactone was polymerized with or without initiator. Several transesterification experiments were conducted at 130 °C, either with polylactide or poly(ε-caprolactone) indicating that several transesterification mechanisms are operating under conditions that do not include formation of cycles by back-biting. Furthermore, reversible polycondensations (revPOCs) with low or moderate conversions were found that did not involve any kind of cyclization. Therefore, These results demonstrate the existence of revPOCs, which do neither obey the theory of irreversible polycondensation as defined by Flory nor the hypothesis of revPOCs as defined by Jacobson and Stockmayer. A new concept encompassing any kind of revPOCs is formulated in the form of a “polycondensation triangle”. KW - Polylactide KW - MALDI-TOF MS KW - Polycondensation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-530831 DO - https://doi.org/10.1039/d1py00704a VL - 12 IS - 35 SP - 5003 EP - 5016 PB - Royal Society for Chemistry AN - OPUS4-53083 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Meyer, A. A1 - Weidner, Steffen T1 - High Tm Poly(l-lactide)s by Means of Bismuth Catalysts? N2 - One series of BiSub-catalyzed ring-opening polymerizations (ROPs) is per-formed at 160 °C for 3 days with addition of difunctional cocatalysts to find out, if poly(l-lactide) crystallizes directly from the reaction mixture. An analogous series is performed with monofunctional cocatalysts. High Tm crystal-lites (Tm > 190 °C) are obtained from all bifunctional cocatalysts, but not from all monofunctional ones. It is shown by means of SAXS measurements that the high Tm values are mainly a consequence of a transesterification–homogenization process across the lamellar surfaces resulting in thickness and smoothing of the surfaces. An unusual enthalpy-driven modification of the molecular weight distribution is found for samples that have crystallized during the polymerization. A third series of ROPs is performed at 170 °C for 2 h followed by annealing at 120 °C (2 h) to induce crystallization. Complete transformation of the resulting low Tm crystallites (Tm < 180 °C) into the high Tm crystallites by annealing at 170 °C for 1 d is not achieved, despite variation of the cocatalyst. KW - Polylactide KW - MALDI-TOF MS KW - Crystallization PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-522777 DO - https://doi.org/10.1002/macp.202100019 SN - 1022-1352 VL - 222 IS - 8 SP - 19 PB - Wiley AN - OPUS4-52277 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - Polymerization of L-lactide with SnCl2: A Low Toxic and Eco-friendly Catalyst N2 - Polymerizations of L-lactide catalyzed either by neat SnCl2 or by SnCl2 + difunctional cocatalysts were conducted in bulk at 180, 160 and 140 °C with variation of the Lac/Cat ratio and time. With neat SnCl2 poly(L-lactide) having weight average molecular weights (uncorrected Mw’s) up to 190 000 g mol−1 were obtained mainly consisting of linear chains. Addition of salicylic acid or 1,1-bisphenol yielded a higher fraction of cyclic polylactides but lower molecular weights. Furthermore, SnCl2 was compared with Bu2SnCl2 and various other metal chlorides and the best results were obtained with SnCl2. With ethyl L-lactate as initiator SnCl2-catalyzed ROPs were performed at 120 °C and the lac/initiator ratio was varied. All these experiments were conducted under conditions allowing for comparison with ROPs catalyzed with neat Sn(II)-2-ethyhexanoate. Such a comparison was also performed with ε-caprolactone as monomer. KW - Catalyst KW - Polylactide KW - MALDI-TOF MS KW - Polycondensation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520517 DO - https://doi.org/10.1007/s10924-020-02042-w SN - 1566-2543 SP - 1 EP - 13 PB - Springer Nature AN - OPUS4-52051 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meyer, A. A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - ROPs of L-lactide catalyzed by neat Tin(II)2-ethylhexanoate - Influence of the reaction conditions on Tm and ΔHm N2 - L-Lactide was polymerized by means of neat SnOct2 with variation of LA/Cat ratio, temperature and time. The resulting cyclic polylactides crystallized spontaneously at 160 °C or below, but needed nucleation via mechanical stress at 165 or 170 °C. All the crystalline polylactides obtained directly from ROP above 120 °C had melting temperatures (Tm) above 189 °C (up to 194.5 °C). SnOct2 also enabled transformation of low Tm poly(L-lactide)s (Tm <180 °C) into the high Tm m1odification by annealing, due to the impact of transesterification reactions in the interphase between the crystallites. The influence of crystallization temperature and annealing time on the crystal thickness was studied via SAXS measurements. A comparison with the crystallization and annealing experiments reported by Pennings and coworkers and Tsuji and Ikada is discussed, and a satisfactory agreement has been found, because those authors also studied polyLA samples containing SnOct2 in its active form. It is also demonstrated in this work that the high Tm modification cannot be obtained when the catalyst is removed or poisoned as it is true for commercial polylactides. KW - Polylactide KW - MALDI-TOF MS KW - Crystallization PY - 2021 DO - https://doi.org/10.1016/j.polymer.2021.124122 SN - 0032-3861 VL - 231 SP - 1 EP - 10 PB - Elsevier CY - Oxford AN - OPUS4-53194 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Falkenhagen, Jana A1 - Kricheldorf, H. R. T1 - SnOct2-catalyzed and alcohol-initiated ROPs of L-lactide – About the influence of initiators on chemical reactions in the melt and the solid state N2 - SnOct2 (Sn(II) 2-ethylhexanoate) catalyzed ROPs of L-lactide were performed in bulk with eight different alcohols as initiators. The time was varied between 1 h and 24 h for all initiators. For two initiators the temperature was also lowered to 115 ◦C. Even-numbered chains were predominantly formed in all polymerizations at short times, but the rate of transesterification (e.g. even/odd equilibration) and the molecular weight distribution were found to depend significantly on the nature of the initiator. Observed transesterification reactions also continued in solid poly (L-lactide), and with the most active initiator, almost total equilibration was achieved even at 130 ◦C. This means that all chains including those of the crystallites were involved in transesterification reactions proceeding across the flat surfaces of the crystallites. The more or less equilibrated crystalline polylactides were characterized by DSC and SAXS measurements with regard to their melting temperature (Tm), crystallinity and crystal thickness. KW - Polylactide KW - MALDI-TOF MS KW - Crystallization KW - Catalysts KW - SAXS PY - 2021 DO - https://doi.org/10.1016/j.eurpolymj.2021.110508 VL - 153 SP - 110508 PB - Elsevier Ltd. AN - OPUS4-52633 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Ring-opening polymerizations of L-Lactide catalyzed by zinc caprylate: Syntheses of cyclic and linear poly(L-lactide)s N2 - Alcohol-initiated ring-opening polymerizations (ROPs) of L-Lactide (LA) were conducted in bulk at 130 °C catalyzed by Zn acetate (ZnAc2), lactate (ZnLac2), or caprylate (ZnCap2). 11-undecenol (UND), 1-hydroxymethylnaphtalene (HMN), and 4-nitrobenzylalcohol (4NB) were used as alcohols. Whereas variation of the alcohols had little effect, the usefulness of the catalysts increased in the order: acetate < lactate < caprylate. Hence, further alcohol-initiated polymerizations were performed with ZnCap2 alone and with variation of the lactide/catalyst (LA/Cat) ratio. With increasing LA/Cat ratio higher fractions of cyclic poly(L-lactide) (PLA) were found, so that the measured degree of polymerization (DP) is considerably lower than the theoretical value (i.e., 2 x LA/alcohol). With neat ZnCap2 cyclic PLAs were the largely prevailing reaction products. For these cyclic PLAs weight average molar masses (Mw) up to 134,000 were obtained and an optical purity around 99% was indicated by 13C NMR spectroscopy and DSC measurements even after 48 h at 150 or 160 °C. KW - Cyclization KW - Lactide KW - Ring opening polymerization KW - Transesterification KW - Zinc catalyst KW - MALDI PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-557565 DO - https://doi.org/10.1002/pol.20220328 SN - 2642-4150 SP - 1 EP - 10 PB - Wiley AN - OPUS4-55756 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - Alcohol-Initiated and SnOct2-Catalyzed Ring-Opening Polymerization (ROP) of L-Lactide in Solution: A Re-investigation N2 - Alcohol-initiated ring-opening polymerizations (ROP) of L-lactide (LA) were studied in solution at 70 °C, whereupon the nature of the alcohol, the LA/initiator ratio, the LA/SnOct2 ratio and the time were varied. In contrast to literature, neat SnOct2 is catalytically active in THF and several aromatic but donor solvents, such as 1,3-dioxolane, dimethylformamide (DMF) or N-methyl pyrrolidone (NMP), strongly reduce the activity of SnOct2. In agreement with literature, no cycles were formed by neat SnOct2 at 70 °C in toluene, whereas almost complete cyclization occurs at 115 °C. This finding is attributed to strongly reduced mobility of the initially formed linear chains having one Sn-O-CH and one anhydride end group. Due to better solvation and enhanced mobility cyclization occurs in THF at 70 °C. KW - Polylactide KW - Ring-opening polymerization KW - MALDI-TOF MS KW - Transesterification PY - 2023 DO - https://doi.org/10.1016/j.eurpolymj.2023.111822 SN - 0014-3057 SP - 1 EP - 18 PB - Elsevier CY - New York, NY [u.a.] AN - OPUS4-56818 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - Dispersities of Polyesters of Various Diphenols Prepared by Irreversible Polycondensations N2 - Polyesters of bisphenol-A, bisphenol-P, catechol, and sebacic acid are prepared and different synthetic methods are compared. The diphenols are condensed with sebacoyl chloride either in dichloromethane/pyridine or in refl uxing chlorobenzene without HCl-acceptor. Further- more, bisphenol-A acetate is polycondensed with sebacic acid in bulk. All experiments are worked up so that fractionation is avoided. The extent of cyclization is estimated by matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) and the molar mass distribution by size exclusion chromatography (SEC). Polycondensations in solution yield larger fractions of cyclics and higher dispersities (up to 11). Polycondensations in bulk give lower fractions of cycles and dispersities from 4.6 to 6.3 for high molar mass polyesters or 2.8 to 3.5 for low molar mass products. Characteristic curves describing the dependence of the dispersity on the initial monomer concentration are elaborated. KW - cyclization KW - dispersity KW - mass spectra KW - polycondensation KW - polyesters PY - 2016 DO - https://doi.org/10.1002/macp.201600004 IS - 217 SP - 1361 EP - 1369 PB - Wiley-VCH Verlag CY - Weinheim AN - OPUS4-37120 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Pasternak, H. A1 - Komann, Steffen ED - Gizejowski, ED - Kozlowski, ED - Sleczka, ED - Ziólko, T1 - A new design formula for determining the load-bearing capacity of locally supported shells T2 - XI. Miedzynarodowa Konferencja Naukowo-Techniczna "Konstrukcje Metalowe" CY - Rzeszów, Poland DA - 2006-06-21 KW - Cylindrical shell KW - Stability KW - Steel KW - Buckling KW - Longitudinal stiffeners PY - 2006 SN - 0-415-40120-8 SP - 160 EP - 161 PB - Taylor & Francis CY - London, UK AN - OPUS4-19152 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Pasternak, H. A1 - Komann, Steffen ED - Camotin, D. T1 - A new approach for determining the load-bearing capacity of locally supported shells N2 - In practice usually thin-walled cylindrical silos are supported locally at the bottom rim of the shell. In this area a stress concentration may occur, which is responisble for buckling of the shell. In the currently applied codes, there is no information, how to analyze the load-bearing capacity of theselocally supported shells. In this paper, a new design formula is given for determining the load-bearing capacity. T2 - International Colloquium on Stability and Ductility of Steel Structures CY - Lisbon, Portugal DA - 2006-09-06 KW - Cylindrical shells KW - Stability KW - Steel KW - Buckling KW - Longiudinal stiffeners PY - 2006 SN - 972-846961-6 VL - 2 SP - 595 EP - 602 PB - IST Press CY - Lisabon AN - OPUS4-19153 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lahcini, M. A1 - Weidner, Steffen A1 - Oumayama, J. A1 - Scheliga, F. A1 - Kricheldorf, H. R. T1 - Unsaturated Copolyesters of Lactide N2 - Four classes of unsaturated copolyesters of L-lactide were prepared either from isosorbide or bis(hydroxymethyl)tricyclodecane in combination with fumaric acid or from 1,4-butenediol or 1,4- butynediol with terephthalic acid. All syntheses were performed in such a way that lactide was oligomerized with a diol as the initiator and the resulting oligomers were polycondensed with a dicarboxylic acid dichloride either in a one-pot synthesis or in a two-step procedure. For most copolyesters the SEC measurements gave weight average molecular weights in the range of 30–60 kg mol⁻1 and dispersities in the range of 4.2–6.2. The MALDI-TOF mass spectra displayed a high content of cycles and indicated an irreversible kinetic course of all polycondensations. Glass-transition temperatures (Tg) above 90 °C were only found for two copolyesters of isosorbide. Addition of bromine to copolyesters of 1,4-butenediol yielded flame retarding biodegradable polymers. KW - Copolyester KW - MALDI-TOF MS KW - SEC KW - Lactide PY - 2016 DO - https://doi.org/10.1039/c6ra16008e VL - 2016/6 IS - 96 SP - 93496 EP - 93504 PB - Royal Society of Chemistry AN - OPUS4-37913 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Salg, Steffen A1 - Malow, Marcus A1 - Morhenn, H. ED - Pierucci, S. ED - Klemes, J.J. T1 - Investigations of deflagration in a four-litre-autoclave under atmospheric and non-atmospheric conditons N2 - A four-litre-autoclave was used to perform deflagration tests in a closed vessel. The aim was to investigate the suitability of this autoclave and to evaluate different parameters influencing the deflagration. The validation of test results showed that the autoclave is suited for the performance of deflagration tests. In comparison to tests performed in an open system according to VDI 2263-1 the results are in good agreement. In the closed vessel same characteristics as in the open test were determined. In addition, pressure rise and rate of pressure rise have been determined and used to characterise deflagrations. The influence of sample weight, tube diameter, bulk density, initial pressure and temperature was investigated. Furthermore, the emerging gas amount and the rate of gas evolution were determined and compared with pressure curves. The use of a four-litre-autoclave for performing deflagration tests offers several advantages in comparison to an open test. T2 - ICheaP12 - International conference on chemical & process engineering CY - Milan, Italy DA - 19.05.2015 KW - Deflagration KW - Closed vessel KW - Autoclave KW - Reduced pressure PY - 2015 UR - http://www.aidic.it/cet/15/43/344.pdf SN - 978-88-95608-34-1 DO - https://doi.org/10.3303/CET1543344 SN - 2283-9216 N1 - Serientitel: Chemical engineering transactions (CEt) – Series title: Chemical engineering transactions (CEt) VL - 43 SP - 2059 EP - 2064 AN - OPUS4-33414 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - High molar mass cyclic poly(L-lactide)s by means of neat tin (II) 2-ethylhexanoate N2 - L-lactide was polymerized in bulk at 120, 140, 160 and 180°C with neat tin(II) 2-ethylhexanoate (SnOct2) as catalyst. At 180°C the Lac/Cat ratio was varied from 25/1 up to 8 000/1 and at 160°C from 25/1 up to 6 000/1. The vast majority of the resulting polylactides consist of cycles in combination with a small fraction of linear chains having one octanoate and one COOH end group. The linear chains almost vanished at high Lac/Cat ratios, as evidenced by MALDI-TOF mass spectrometry and measurements of intrinsic viscosities and dn/dc values. At Lac/Cat ratios <1000/1 the number average molar masses (Mn) are far higher than expected for stoichiometic initiation, and above 400/1 the molar masses vary relatively little with the Lac/Cat ratio. At 180° slight discoloration even at short times and degradation of the molar masses were observed, but at 160°C or below colorless products with weight average molar masses (Mw) up to 310 000 g mol-1 were obtained. The formation of high molar mass cyclic polylactides is explained by a ROPPOC (Ring-Opening Polymerizatiom with simultaneous Polycondensation) mechanism with intermediate formation of linear chains having one Sn-O-CH end group and one mixed anhydride end group. Additional experiments with tin(II)acetate as catalyst confirm this interpretation. These findings together with the detection of several transesterification mechanisms confirm previous critique of the Jacobson-Stockmayer theory. KW - Polylactide KW - MALDI-TOF MS KW - Cyclization PY - 2020 DO - https://doi.org/10.1039/d0py00811g VL - 11 IS - 32 SP - 5249 EP - 5260 PB - Royal Society for Chemistry AN - OPUS4-51130 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - The Ring-Opening Polymerisation-Polycondensation (ROPPOC) Approach to cyclic Polymers N2 - A new concept called “Ring-Opening Polymerization (ROP) combined with simultaneous POlyCondensation” (ROPPOC) is presented and discussed. This synthetic strategy is based on the intermediate formation of chains having two end groups that can react with each other. The ROPPOC syntheses are subdivided into three groups according to the nature of the chain ends: two ionic end groups, one ionic and one covalent chain end and a combination of two reactive covalent end groups may be involved, depending on the catalyst. The usefulness for the preparation of cyclic polymers is discussed with a review of numerous previously published examples. These examples concern to following classes of cyclic polymers: polypeptides, polyamides, polyesters, including polycarbonates, and cyclic polysiloxanes. It is demonstrated, that the results of certain ROPPOC syntheses are in contradiction to the Jacobson-Stockmayer theory. Finally, the usefulness of ROPPOCs for the detection of polydisperse catenanes is discussed. KW - Ring-opening Polymerisation KW - MALDI-TOF MS KW - ROPPOC KW - Cyclic PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508509 DO - https://doi.org/10.1002/marc.202000152 SP - 2000152 PB - Wiley AN - OPUS4-50850 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Salg, Steffen A1 - Malow, Marcus A1 - Morhenn, H. T1 - Experimentelle und theoretische Untersuchung des Zersetzungsmechanismus deflagrationsfähiger Substanzen N2 - In einem Vier-Liter-Autoklaven wurden erstmals Untersuchungen zu Deflagrationen von Azodicarbonamid durchgeführt. Aus den Arbeiten lässt sich folgern, dass der Vier-Liter-Autoklav zur Bestimmung und Beschreibung der Deflagrationsfähigkeit von Azodicarbonamid gut geeignet ist und im Vergleich zu Messungen inoffenen Prüfanordnungen eine Reihe von Vorteilen bietet. KW - Deflagration KW - Geschlossener Behälter KW - Autoklav KW - Gas- und Druckmengenmessung PY - 2015 SN - 2191-0073 VL - 5 IS - 6 SP - 39 EP - 44 PB - Springer-VDI-Verl. CY - Düsseldorf AN - OPUS4-33491 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Doriti, A. A1 - Brosnan, S. A1 - Weidner, Steffen A1 - Schlaad, H. T1 - Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base N2 - Polysarcosine (M-n = 3650-20 000 g mol(-1), D similar to 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator. KW - Polysarcosine KW - MALDI-TOF MS KW - Synthesis PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-359309 DO - https://doi.org/10.1039/c6py00221h SN - 1759-9954 SN - 1759-9962 VL - 7 IS - 18 SP - 3067 EP - 3070 AN - OPUS4-35930 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, H. R. T1 - Matrix-assisted laser desorption/ionization behavior of neat linear and cyclic poly(L-lactide)s and their blends N2 - Numerous new tin catalysts that enable the synthesis of cyclic polylactides with broad variation in their molecular mass were recently developed. The abundance of cyclics in matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra is, however, frequently reported to greatly exceed that of linears. Thus, the MALDI ionization behavior of various end-capped linear poly(L-lactide)s and one cyclic poly(L-lactide) was investigated and compared. Neat compounds and various blends of cyclic and linear species were prepared and studied under identical conditions with regard to sample preparation and instrumental condition, except for the laser power. For this purpose, two different MALDI-TOF mass spectrometers were applied. Our results reveal that cyclics indeed show a slightly better ionization in MALDI, although their ionization as a neat compound seems to be less effective than that of linear polylactides. The ionization of most linear polylactides investigated does not depend on the end group structure. However, linear polylactides containing 12-bromododecyl end groups reveal an unexpected saturation effect that is not caused by fragmentation of the polymer or the end group, or by electronic saturation of the detector digitizer. Furthermore, polylactides with a 2-bromoethyl end group did not show such a saturation effect. An overestimation of cyclic species in MALDI-TOF mass spectra of poly(L-lactide)s must be considered, but the commonly assumed peak suppression of linear polymers in mixtures of both structures can be excluded. KW - Polylactide KW - MALDI-TOF MS KW - Blends KW - Ionization PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504216 DO - https://doi.org/10.1002/rcm.8673 VL - 34 SP - e8673 PB - Wiley Online Libary AN - OPUS4-50421 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Synthesis of cyclic polymers and flaws of the Jacobson–Stockmayer theory N2 - Cyclic poly(L-lactide)s were prepared by ring-opening polymerization combined with simultaneous polycondensation (ROPPOC) in bulk at 160 ° with dibutyltin bis(4-cyanophenoxide) as catalyst. It is demonstrated by MALDI TOF mass spectrometry and 1H NMR end group analyses that cycles are formed by endto-end cyclization in addition to “back-biting” transesterification. Formation of high molar mass cyclic poly L-lactide)s by means of several more reactive ROPPOC catalysts presented previously and in new experiments is discussed. These experimental results, together with theoretical arguments, prove that part of the Jacobson–Stockmayer theory is wrong. The critical monomer concentration, above which end-toend cyclization is seemingly impossible, does not exist and reversible like irreversible polycondensations can theoretically proceed up to 100% conversion, so that finally all reaction products will necessarily adopt a cyclic architecture. KW - Polylactide KW - MALDI-TOF MS KW - Cyclization PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506419 DO - https://doi.org/10.1039/d0py00226g VL - 11 IS - 14 SP - 2595 EP - 2604 PB - Royal Society for Chemistry AN - OPUS4-50641 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Kricheldorf, H. R. T1 - Ring–Ring Equilibration in Solid, Even-Numbered Cyclic Poly(l-lactide)s and their Stereocomplexes N2 - Even-numbered cyclic poly(d-lactide) and poly(l-lactide) are prepared by ringexpansion polymerization. The cyclic pol(l-lactide) is annealed either at 120 or at 160 °C for several days. The progress of transesterification in the solid state is monitored by the formation of odd-numbered cycles via matrix-assisted laser desorption/ionization-time of flight mass spectrometry. The changes of the crystallinity are monitored by differential scanning calorimetry, wideand small-angle x-ray scattering (WAXS and SAXS) measurements. Despite total even-odd equilibration at 160 °C, the crystallinity of poly(l-lactide) is not reduced. Furthermore, the crystallinity of the stereocomplexes of both cyclic polylactides do not decrease or vanish, as expected, when a blocky or random stereosequence is formed by transesterification. This conclusion is confirmed by 13C NMR spectroscopy. These measurements demonstrate that transesterification is a ring–ring equilibration involving the loops on the surfaces of the lamellar crystallites thereby improving crystallinity and 3D packing of crystallites without significant broadening of the molecular weight distribution. KW - Polylactide KW - MALDI-TOF MS KW - Cyclization PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-506458 DO - https://doi.org/10.1002/macp.202000012 VL - 221 IS - 9 SP - 2000012 PB - Wiley-VCH Verlag AN - OPUS4-50645 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen T1 - SnOct 2-Catalyzed Syntheses of Cyclic Poly (l-lactide) s with Catechol as Low-Toxic Co-catalyst N2 - Polymerizations of l-lactide in bulk at 160 or 180 °C were performed with 1/1 mixtures of catechol (CA) or 4-tert-butylcatechol (BuCA) and tin(II)-2-ethylhexanoate (SnOct2) as catalysts and a variation of the Lac/Cat ratio. Weight average molar masses (Mw) up to 170,000 g mol−1 were obtained with CA and up to 120,000 g mol−1 with BuCA. The cyclic structure of the resulting poly(l-lactide)s was proven by MALDI-TOF mass spectrometry and by comparison of their hydrodynamic volumes with those of commercial linear poly(l-lactide)s. The predominance of even-numbered cycles increased with lower temperatures and shorter polymerization times. This fnding indicates that the cyclic architecture is the results of a ring-expansion polymerization mechanism. Addition of silylated BuCA as co-catalyst was less favorable than addition of free BuCA. KW - Polylactide KW - MALDI-TOF MS KW - Cyclization KW - Catalyst KW - Catechol KW - Toxicity PY - 2019 DO - https://doi.org/10.1007/s10924-019-01545-5 SP - 10924 PB - Springer AN - OPUS4-49210 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Meyer, A. T1 - High Tm poly(L-lactide)s via REP or ROPPOC of L-lactide N2 - A new kind of high melting (HTm) pol(L-lactide) was discovered when cyclic poly(L-lactide)s were prepared by ring-expansion polymerization with cyclic tin catalysts at 130–160 °C in bulk. By DSC measurements with 10 K min−1 melting temperatures (Tm) in the range of 190–196 °C were found. The WAXS and SAXS measurements evidenced that not a new crystal lattice but a well-ordered morphology and a higher perfection of the crystallites are responsible for the high Tm values and high crystallinities. Under identical reaction conditions SnOct2-catalyzed and alcohol-initiated ROPs do not yield these crystallites. Furthermore, it was found that the standard crystallites are kinetically favored upon rapid crystallization, whereas the high melting form of poly(L-lactide) is thermodynamically more stable. KW - Polylactide KW - MALDI-TOF MS KW - ROPPOC PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-507477 DO - https://doi.org/10.1039/c9py01908a VL - 11 IS - 12 SP - 2182 EP - 2193 PB - Royal Society of Chemistry AN - OPUS4-50747 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Synthesis of cyclic poly(l-lactide) catalyzed by Bismuth salicylates-A combination of two drugs N2 - l‐lactide was polymerized in bulk at 160 or 180°C with mixtures of bismuth subsalicylate (BiSub) and salicylic (SA) as catalysts. The SA/Bi ratio and the monomer/Bi ratio were varied. The highest molecular weights (weight average, Mw) were achieved at a SA/Bi ratio of 1/1 (Mw up to 92 000 g mol−1). l‐Lactide was also polymerized with combinations of BiSub and silylated SA, and Mw values up to 120 000 g mol−1 were achieved at 180°C. MALDI‐TOF mass spectrometry and Mark‐Houwink‐Sakurada measurements proved that under optimized reaction conditions the resulting polylactides consist of cycles. KW - Polylactide KW - MALDI-TOF MS KW - Cyclization KW - Catalyst KW - Salicylate PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-488622 DO - https://doi.org/10.1002/pola.29473 SN - 0887-624X SN - 1099-0518 SP - 29473 PB - Wiley AN - OPUS4-48862 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - Reply to the comment on “synthesis of cyclic polymers and flaws of the Jacobson-Stockmayer theory” by R. Szymanski N2 - In a recent publication the authors have presented theoretical and experimental results indicating that the Jacobson–Stockmayer (JS) theory does not provide a correct description of reversible polycondensations for all polymers and for high conversions (e.g. polycondensation in bulk). In this context reversibility means that all condensation step whether resulting in chain growth or in cyclization are reversible and thus, part of an equilibrium. The first two sections of that paper were focused on the demonstration that small, and above all, large cycles can be formed by end-to-end (ete) cyclization in reversible like in irreversible polycondensations. A significant contribution of ete-cyclization to the course of reversible polycondensations was denied by J + S apparently as a contribution to Florýs dogma, that the end groups of long polymer chains will never meet. KW - Polylactide KW - MALDI-TOF MS KW - Jacobsen-Stockmayer theory PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-513985 DO - https://doi.org/10.1039/D0PY01118E VL - 11 IS - 38 SP - 6226 EP - 6228 PB - Royal Society of Chemistry AN - OPUS4-51398 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Chatti, S. A1 - Kricheldorf, H. R. T1 - About the transformation of low Tm into high Tm poly(L-lactide)s by annealing under the influence of transesterification catalysts N2 - Cyclic polylactides were prepared in bulk at 170 °C, crystallized at 120 °C and then annealed at temperatures between 130 and 170 C with variation of catalyst, catalyst concentration and annealing time. The transformation of the initially formed low melting (LTm) crystallites, having melting temperatures (Tm) <180 °C into high melting (HTm) crystallites having Tm values > 189 °C was monitored by means of DSC measurements and characterized in selected cases by SAXS measurements. It was confirmed that the formation of HTm crystallites involves a significant growth of the thickness of the lamellar crystallites along with smoothing of their surface. Annealing at 170 °C for 1 d or longer causes thermal degradation with lowering of the molecular weights, a gradual transition of cyclic into linear chains and a moderate decrease of lamellar thickness. An unexpected result revealed by MALDI TOF mass spectrometry is a partial reorganization of the molecular weight distribution driven by a gain of crystallization enthalpy. KW - Polylactide KW - MALDI-TOF MS KW - Crystallization KW - Annealing PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-521062 DO - https://doi.org/10.1039/d0ra10012a VL - 11 IS - 5 SP - 2872 EP - 2883 PB - Royal Society of Chemistry AN - OPUS4-52106 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - ROP of L-lactide and ε-caprolactone catalyzed by tin(ii) and tin(iv) acetates–switching from COOH terminated linear chains to cycles N2 - The catalytic potential of tin(II)acetate, tin(IV)acetate, dibutyltin-bis-acetate and dioctyl tin-bis-acetate was compared based on polymerizations of L-lactide conducted in bulk at 160 or 130C. With SnAc2 low-Lac/Cat ratios (15/1–50/1) were studied and linear chains having one acetate and one carboxyl end group almost free of cyclics were obtained. Higher monomer/catalyst ratios and lower temperatures favored formation of cycles that reached weight average molecular weights (Mw's) between 100,000 and 2,500,000. SnAc4 yielded mixtures of cycles and linear species under all reaction conditions. Dibutyltin- and dioctyl tin bis-acetate yielded cyclic polylactides under most reaction conditions with Mw's in the range of 20,000–80,000. Ring-opening polymerizations performed with ε-caprolactone showed similar trends, but the formation of COOH-terminated linear chains was significantly more favored compared to analogous experiments with lactide. The reactivity of the acetate catalysts decreased in the following order: SnAc2> SnAc4>Bu2SnAc2 Oct2SnAc2. KW - Catalyst KW - MALDI-TOF MS KW - Ring-opening polymerization KW - Tin acetates KW - Polylactide PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520831 DO - https://doi.org/10.1002/pol.20200866 SP - 1 EP - 12 PB - Wiley Online Library AN - OPUS4-52083 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meyer, A. A1 - Weidner, Steffen A1 - Kricheldorf, H. T1 - Stereocomplexation of cyclic polylactides with each other and with linear poly(L-lactide)s N2 - Two kinds of cyclic poly(D- and L-lactide)s were synthesized, namely CI labeled samples mainly consisting of even-numbered cycles with low dispersity and CII, CIII or CIV-labeled ones consisting of equal amounts of even and odd-numbered cycles with high dispersity and igher molecular weights (Mw up to 300 000). Furthermore, linear poly L-lactide)s were prepared by initiation with ethanol and in both series the molecular weight was varied. The formation of stereocomplexes from cyclic poly(D-lactide)s and all kinds of poly L-lactide)s was performed in dichloromethane/toluene mixtures. The stereocomplexes crystallized from the reaction mixture were characterized in the virgin state and after annealing at 205 °C. Stereocomplexes free of stereohomopolymers with crystallinities up to 80% were obtained from all experiments in yields ranging from 60 to 80%. Despite the high annealing temperature (maintained for 1 h), little transesterification was observed and the crystallinity slightly increased. KW - Polylactide KW - MALDI-TOF MS KW - Stereocomplex KW - Cyclic PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-496693 DO - https://doi.org/10.1039/c9py01236b VL - 10 SP - 6191 EP - 6199 PB - Royal Society for Chemistry AN - OPUS4-49669 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, H. R. A1 - Scheliga, F. T1 - Ring-expansion copolymerization of L-lactide and glycolide N2 - 1:1 Copolymerizations of glycolide (GL) and L-lactide (LA) is performed in bulk at 100°C and at 160°C with four cyclic tin catalysts. The resulting copolyesters are characterized by SEC measurements, 1H and 13C NMR spectroscopy and by MALDI TOF mass spectrometry. At 160°C and longer reaction time (22 h) nearly complete conversion of both monomers is achieved, and cyclic copolymers with nearly random sequences are formed. At shorter times (0.5-3.0 h, depending on catalyst) the conversion of LA is incomplete, and only cyclics having even numbers of lactyl units are obtained. At 100°C at 22 h again cycles mainly consisting of even numbered lactyl units are formed, but with even and odd numbers of glycolyl units. Copolymerization of lactide at 160°C with small amounts of GL show that formation of high Tm crystallites (Tm > 190°C) is hindered even when only > 2% of GL is added. For polyglycolide containing a smaller amount of lactide complete solubility in hexafluoroisopropanol is only observed around and above 20 mol% of lactide. KW - Ring-expansion polymerization KW - Copolymerization KW - MALDI-TOF MS KW - L-lactide KW - Glycolide KW - Crystallization PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-520270 DO - https://doi.org/10.1002/macp.202000307 SN - 1022-1352 VL - 22 IS - 3 SP - 307 PB - WileyVCH AN - OPUS4-52027 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - High molecular weight poly(l-lactide) via ring-opening polymerization with bismuth subsalicylate-The role of cocatalysts N2 - The catalytic potential of bismuth subsalicylate (BiSub), a commercial drug, for ring-opening polymerization (ROP) of L-lactide was explored by variation of co-catalyst and polymerization time. Various monofunctional phenols or carboxylic acids, aromatic ortho-hydroxy acids and diphenols were examined as potential co-catalysts. 2,2´-Dihydroxybiphenyl proved to be the most successful co-catalyst yielding weight average molecular weights (uncorrected Mw values up to 185 000) after optimization of reaction time and temperature. Prolonged heating (>1-2h) depending on catalyst concentration) caused thermal degradation. In polymerization experiments with various commercial Bi(III) salts a better alternative to BiSub was not found. By means of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry a couple of unusual and unexpected transesterification reactions were discovered. Finally, the effectiveness of several antioxidants and potential catalyst poisons was explored, and triphenylphosphine was found to be an effective catalyst poison. KW - Polylactide KW - MALDI-TOF MS KW - Ring-opening polymerization KW - Bismuth PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-519513 DO - https://doi.org/10.1002/app.50394 SN - 0021-8995 VL - 138 IS - 19 SP - 50394 PB - Wiley AN - OPUS4-51951 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Meyer, A. T1 - High Tm linear poly(L-lactide)s prepared via alcohol-initiated ROPs of L-lactide N2 - Alcohol-initiated ROPs of L-lactide were performed in bulk at 160 °C for 72 h with variation of the catalyst or with variation of the initiator (aliphatic alcohols). Spontaneous crystallization was only observed when cyclic Sn(II) compounds were used as a catalyst. Regardless of initiator, high melting crystallites with melting temperatures (Tm) of 189–193 °C were obtained in almost all experiments with Sn(II) 2,2′-dioxybiphenyl (SnBiph) as catalyst, even when the time was shortened to 24 h. These HTm poly(lactide)s represent the thermodynamically most stable form of poly(L-lactide). Regardless of the reaction conditions, such high melting crystallites were never obtained when Sn(II) 2-ethylhexanoate (SnOct2) was used as catalyst. SAXS measurements evidenced that formation of HTm poly(L-lactide) involves growth of the crystallite thickness, but chemical modification of the crystallite surface (smoothing) seems to be of greater importance. A hypothesis, why the “surface smoothing” is more effective for crystallites of linear chains than for crystallites composed of cycles is discussed. KW - Polylactide KW - MALDI-TOF MS KW - Ring-opening polymerization PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524330 DO - https://doi.org/10.1039/d1ra01990b VL - 11 IS - 23 SP - 14093 EP - 14102 PB - Royal Society of Chemistry AN - OPUS4-52433 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - ROP of L-lactide and ε-caprolactone catalyzed by tin(ii) andtin(iv) acetates–switching from COOH terminated linear chains to cycles N2 - The catalytic potential of tin(II)acetate, tin(IV)acetate, dibutyltin-bis-acetate and dioctyl tin-bis-acetate was compared based on polymerizations of L-lactide conducted in bulk at 160 or 130°C. With SnAc2 low-Lac/Cat ratios (15/1–50/1) were studied and linear chains having one acetate and one carboxyl end group almost free of cyclics were obtained. Higher monomer/catalyst ratios and lower temperatures favored formation of cycles that reached weight average molecular weights (Mw's) between 100,000 and 2,500,000. SnAc4 yielded mixtures of cycles and linear species under all reaction conditions. Dibutyltin- and dioctyl tin bis-acetate yielded cyclic polylactides under most reaction conditions with Mw's in the range of 20,000–80,000. Ring-opening polymerizations performed with ε-caprolactone showed similar trends, but the formation of COOH-terminated linear chains was significantly more favored compared to analogous experiments with lactide. The reactivity of the acetate catalysts decreased in the following order: SnAc2> SnAc4>Bu2SnAc2~Oct2SnAc2 KW - Polylactide KW - MALDI-TOF MS KW - Catalyst KW - Ring-opening polymerization KW - Tin acetates PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-521923 DO - https://doi.org/10.1002/pol.20200866 VL - 59 IS - 5 SP - 439 EP - 450 PB - Wiley Online Library AN - OPUS4-52192 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Scheliga, F. A1 - Weidner, Steffen T1 - What does conversion mean in polymer science? N2 - The definition of the term “conversion” is discussed for a variety of polymer syntheses. It is demonstrated that in contrast to organic and inorganic chemistry several different definitions are needed in polymer science. The influence of increasing conversion on structure and topology of homo- and Copolymers is illustrated. Chain-growth polymerizations, such as radical polymerization or living anionic polymerizations of vinyl monomers, condensative chain polymerization, two and three-dimensional step-growth polymerizations, ring–ring or chain–chain equilibration and chemical modification of polymers are considered. KW - Polymers KW - Polymerization KW - Conversion KW - Polycondensation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523597 DO - https://doi.org/10.1002/macp.202100010 VL - 222 IS - 8 SP - 10 PB - Wiley VCH AN - OPUS4-52359 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, H. R. T1 - The Role of Transesterification in SnOct 2 - Catalyzed Polymerizations of Lactides N2 - l-lactide or meso-lactide are polymerized either at 120 °C where the polymerization process of l-lactide is accompanied by crystallization, or at 180 °C where poly(l-lactide) remains in the molten state. Polymerizations at 120 °C initially yield even-numbered chains (with respect to lactic acid units) having relatively low dispersity, but the fraction of odd-numbered chains increases with time and the entire molecular weight distribution changes. Traces of cyclics are only formed after 7 d. Polymerizations at 180 °C yield equilibrium of even and odd-numbered chains from the beginning, but at low monomer/initiator ratios and short reaction times (<4 h) cyclics are again not formed. They appear at longer reaction times and entail higher dispersities. The results are discussed in terms of five different transesterification mechanisms. KW - Polylactides KW - MALDI KW - Transesterification KW - Sn catalysts PY - 2017 DO - https://doi.org/10.1002/macp.201600331 SN - 1022-1352 VL - 218 IS - 3 SP - 1600331 PB - Wiley AN - OPUS4-39753 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Cyclic poly(L-lactide)s via ring-expansion polymerizations catalysed by 2,2-dibutyl-2- stanna-1,3-dithiolane N2 - L-Lactides were polymerized in bulk at 120 or 160 °C with cyclic dibutyltin catalysts derived from 1,2-dimercaptoethane or 2-mercaptoethanol. Only linear chains having one benzyl ester and one OH-end group were obtained when benzyl alcohol was added. When L-lactides were polymerized with neat dibutyl-2-stanna-1,3-dithiolane, exclusively cyclic polylactides were formed even at 120 °C. The temperature, time and monomer/catalyst ratio (M/C) were varied. These results are best explained by a combination of ring-expansion polymerization and ring-extrusion of cyclic oligo- or polylactides with Elimination of the cyclic catalyst. Neither syntheses of linear polylactides nor of cyclic lactides involved racemization up to 20 h at 160 °C. KW - Ring-expansion polymerization KW - MALDI KW - Polylactides PY - 2017 DO - https://doi.org/10.1039/C6PY02166B SN - 1759-9954 SN - 1759-9962 VL - 8 IS - 9 SP - 1589 EP - 1596 PB - Royal Society of Chemistry AN - OPUS4-39748 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Cyclic poly(lactide)s via the ROPPOC method catalyzed by alkyl- or aryltin chlorides N2 - A comparison of tributyltin chloride, dibutyltin dichloride,and butyltin trichloride as catalysts of ring-opening polymerizations(ROPs) of l-lactides at 160°C in bulk reveals increasing reactivity in the above order, but only the least reactive catalysts, Bu3SnCl, yield a uniform reaction product, namely cyclic poly(L-lactide)s with weight average molecular weights (Mw ́s) in the range of 40,000–80,000. A comparison of dimethyltin , dibutyltin , and diphenyltin dichlorides resulted in the following order of reactivity: Me2SnCl2120 °C, but different results at 100 or 80 °C. Surprisingly, bell-shaped narrow molecular weight distributions are obtained <140 °C, resembling the pattern of living polymerizations found for alcohol-initiated polymerizations. An unusual transesterification mechanism yielding narrow distributions of odd-numbered cycles is discovered too. KW - Cyclization KW - Polylactides KW - MALDI-TOF MS KW - Ring-opening polymerization KW - Spirocyclic PY - 2018 DO - https://doi.org/10.1002/pola.29259 SN - 0887-624X SN - 1099-0518 VL - 56 IS - 24 SP - 2730 EP - 2738 PB - Wiley Periodicals AN - OPUS4-46498 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - About formation of cycles in Sn(II) octanoate-catalyzed polymerizations of lactides N2 - At first, formation of cycles in commercial poly(Llactide)s is discussed and compared with benzyl alcoholinitiated polymerizations performed in this work. This comparison was extended to polymerizations initiated with 4-cyanophenol and pentafluorothiophenol which yielded cyclic polylactides via end-biting. The initiator/catalyst ratio and the acidity of the initiator were found to be decisive for the extent of cyclization. Further polymerizations of L-lactide were performed with various diphenols as initiators/co-catalysts. With most diphenols, cyclic polylactides were the main reaction products. Yet, only catechols yielded even-numbered cycles as main reaction products, a result which proves that their combination with SnOct2 catalyzed a ring-expansion polymerization (REP). The influence of temperature, time, co-catalyst, and catalyst concentrations was studied. Four different transesterification reactions yielding cycles were identified. For the cyclic poly(L-lactide)s weight average molecular weights (Mw’s) up to 120,000 were obtained, but 1H NMR end group analyses indicated that the extent of cyclization was slightly below 100%. The influence of various parameters like structure of Initiator and catalyst and temperature on the formation of cyclic poly(Llactide)s has been investigated. Depending on the chosen conditions, the course of the polymerization can be varied from a process yielding exclusively linear polylactides to mainly cyclic polylactides. Three different reaction pathways for cyclization reactions have been identified. KW - Cyclization KW - MALDI-TOF MS KW - Polyester KW - Ring-opening polymerization KW - Transesterification PY - 2018 DO - https://doi.org/10.1002/pola.29077 SN - 0887-624X VL - 56 IS - 17 SP - 1915 EP - 1925 PB - Wiley Periodicals Inc. AN - OPUS4-46052 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - Cyclic poly(L-lactide)s via simultaneous ROP and polycondensation (ROPPOC) catalyzed by dibutyltin phenoxides N2 - Starting from dibutyltin oxide, four catalysts were synthesized, namely the dibutyltin bisphenoxides of Phenol (SnPh), 4-chlorophenol (SnCP), 4-hydroxybenzonitrile (SnCN) and pentafluorophenol (SnOPF). With the first three catalysts polymerizations of L-lactide at 160 °C in bulk yielded large fraction of linear chains having phenylester end groups at short reaction times. At longer times the fraction of cycles considerably increased at the expense of the linear chains, when SnCN was used as catalyst. With SnOPF only cyclic polylactides were obtained at low Lac/Cat ratios (< 400) with weight average molecular weights (Mw) up to 90 000 Da, whereas for high Lac/Cat ratios mixtures of cyclic and linear chains were found. Polymerizations in solution enabled variation of the molecular weight. Polymerizations of meso-lactide at temperatures down to 60 °C mainly yielded even-numbered linear chains supporting the postulated ROPPOC mechanism. KW - Cyclization KW - MALDI-TOF MS KW - Polycondensation KW - Ring-opening Polymerization KW - Polylactide PY - 2018 DO - https://doi.org/10.1016/j.eurpolymj.2018.10.005 SN - 0014-3057 IS - 109 SP - 360 EP - 366 PB - Elsevier AN - OPUS4-46263 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, H. T1 - Transesterification in alcohol-initiated ROPs of l- and meso-lactide catalyzed by Sn(II) and Sn(IV) compounds at low temperatures N2 - The purpose of this study is to shed more light on the transesterification processes in alcohol-initiated and tin(II) 2-ethylhexanoate (SnOct2)-catalyzed polymerizations of lactides at low or moderate temperatures. Ethanol-initiated polymerizations are conducted in concentrated solutions at 80 °C and a strong dependence of even/odd equilibration on the alcohol/Sn ratio. Around or above 120 °C cyclization of poly(l-lactide) via “backbiting” occurs as a third mechanism. However, poly(m-lactide) shows a higher cyclization tendency and yields cyclics even at 100 °C. Combinations of ethanol and certain cyclic dibutyltin(IV) catalysts also yield cyclic oligomers of l-lactide at 80 °C. Reaction conditions allowing for a total suppression of all transesterification reactions are not found, but even-numbered poly(m-lactide)s with a purity >95% are obtained at 70 or 60 °C. KW - Cyclization KW - MALDI-TOF MS KW - Polyester KW - Polylactide KW - Transesterification PY - 2018 DO - https://doi.org/10.1002/macp.201800445 SN - 1022-1352 SN - 1521-3935 VL - 219 IS - 24 SP - 1800445, 1 EP - 10 PB - Wiley-VCH CY - Weinheim AN - OPUS4-46705 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Meyer, A. T1 - Syntheses of Polyglycolide via Polycondensation: A Reinvestigation N2 - The Na salt of chloroacetic acid is condensed in suspension. Furthermore,glycolic acid is condensed in bulk or in concentrated solution by means of SnCl2 or 4-toluene sulfonic acid (TSA) as catalysts. The temperatures are varied from 160 to 200°C and the time from 1 to 5 days. Low molar mass cyclic poly(glycolic acid) (PGA) is detected by means of matrix-assisted laser desorption ionization time-of-flight (MALDI TOF) mass spectrometry in most PGAs. A predominance of certain cycles having an even number of repeat units is observed suggesting a thermodynamically favored formation of extended-ring crystals. Extremely high melting temperatures (up to 237.5°C)and high melting enthalpies are found for polycondensations with TSA in 1,2-dichlorobenzene. KW - MALDI TOF MS KW - Polycondensation KW - Polyglycolide KW - Cyclization PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-596856 DO - https://doi.org/10.1002/macp.202300397 IS - 2300397 SP - 1 EP - 7 PB - Wiley VHC-Verlag AN - OPUS4-59685 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Kricheldorf, H. T1 - Cyclic polyglycolides via ring-expansion polymerization with cyclic tin catalysts N2 - Glycolide was polymerized in bulk with two cyclic catalysts − 2,2-dibutyl-2-stanna-1,3-dithiolane (DSTL) and 2-stanna-1,3-dioxa-4,5,6,7-dibenzepane (SnBiph). The monomer/initiator ratio, temperature (140 – 180 °C) and time (1–––4 days) were varied. The MALDI TOF mass spectra exclusively displayed peaks of cyclic polyglycolide (PGA) and revealed an unusual “saw-tooth pattern” in the mass range below m/z 2 500 suggesting formation of extended ring crystallites. The DSC measurements indicated increasing crystallinity with higher temperature and longer time, and after annealing for 4 d at 160 °C a hitherto unknown and unexpected glass transition was found in the temperature range of 170–185 °C. Linear PGAs prepared by means of metal alkoxides under identical conditions did not show the afore-mentioned features of the cyclic PGAs, neither in the mass spectra nor in the DSC measurements. All PGAs were also characterized by SAXS measurements, which revealed relatively small L-values suggesting formation of thin crystallites in all cases with little influence of the reaction conditions. KW - Polyglycolide KW - MALDI-TOF MS KW - Ring-expansion polymerization KW - Crystals PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-595541 DO - https://doi.org/10.1016/j.eurpolymj.2024.112811 SN - 0014-3057 VL - 207 SP - 1 EP - 9 PB - Elsevier Ltd. AN - OPUS4-59554 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Meyer, A. T1 - Syntheses of high molecular mass polyglycolides via ring-opening polymerization with simultaneous polycondensation(ROPPOC) by means of tin and zinc catalysts N2 - Glycolide was polymerized in bulk by means of four different ROPPOC catalysts: tin(II) 2-ethylhexanoate (SnOct2), dibutyltin bis(pentafluoro-phenoxide) (BuSnOPF),zinc biscaproate (ZnCap), and zinc bis(pentafluoro-phenyl sulfide) (ZnSPF). The temperature was varied between 110 and 180°C and the time between 3 h and 7 days. For the few polyglycolides (PGAs) that were soluble extremely high molecular masses were obtained. The MALDI TOF mass spectra had all a low signal-to-noise ration and displayed the peaks of cyclic PGAs with a“saw-tooth pattern ”indicating formation of extended-ring crystallites in the mass range below m/z 2500. The shape of DSC curves varied considerably with catalyst and reaction conditions, whereas the long-distance values measured by SAXS were small and varied little with the polymeriza-tion conditions. KW - MALDI TOF MS KW - Polyglycolide KW - Crystalinity PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598221 DO - https://doi.org/10.1002/pat.6365 VL - 35 IS - 4 SP - 1 EP - 10 PB - John Wiley & Sons Ltd. AN - OPUS4-59822 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Polycondensation of poly(L-lactide) alkyl esters combined with disproportionation and symproportionation of the chain lengths N2 - Ring-opening polymerizations (ROPs) of l-lactide (LA) were performed with ethyl l-lactate or 11-bromoundecanol as initiators (In) and tin(II) ethyl hexanoate (SnOct2) as catalyst (Cat) using four different LA/In ratios (20/1, 40/1, 60/1, and 100/1). One series of ROPs was conducted in bulk at 120 °C, yielding PLAs with low dispersities (Ð ~ 1.2–1.4), and a second series was conducted in bulk at 160 °C, yielding higher dispersities (Ð ~ 1.3–1.9). Samples from both series were annealed for 1 or 14 days at 140 °C in the presence of SnOct2. Both polycondensation and disproportionation reactions occurred, so that all four samples tended to form the same type of molar mass distribution below 10,000 Da, regardless of their initially different number average molar masses (Mn). Both initiators gave nearly identical results. The thermodynamic control of all reversible transesterification processes favored the formation of crystallites composed of chains with a Mn around 3500–3700, corresponding to a crystal thickness of 10–13 nm. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-600081 DO - https://doi.org/10.1002/pol.20240118 SN - 2642-4150 SP - 1 EP - 12 PB - Wiley AN - OPUS4-60008 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Scheliga, F. A1 - Weidner, Steffen T1 - Syntheses of Cyclic Poly(l-lactide)s by Means of Zinc-Based Ring-Opening Polymerization with Simultaneous Polycondensation (ROPPOC) Catalysts N2 - Ring-opening polymerizations of l-lactide are studied in bulk at 140 or 160 °C with zinc n-hexanoate, zinc 4-chlorothiophenolate, and zinc pentafluoro thiophenolate (ZnSPF) as catalysts. The reactivity increases in the given order. With all three catalysts a high fraction of cycles is obtained only at polymerization (annealing) times around 7 d. With ZnSPF weight average molecular weights (Mw) up to 178 000, a Tm around 199 °C and a 𝚫Hm around 99 J g−1 were achieved. The samples annealed for 4 or 7 d also display a saw tooth pattern of the mass peak distribution in the matrix-assisted laser desorption/ionization time of flight spectra indicating transesterification reactions across the surface of extended ring crystals. This process optimizes the thermodynamical properties of the crystalline cyclic polylactides and is responsible for the high Tm and 𝚫Hm values. KW - Polylactide KW - MALDI-TOF MS KW - Ring opening polymerization KW - Polymerization PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-578264 DO - https://doi.org/10.1002/macp.202300070 SN - 1022-1352 SP - 202300070 PB - Wiley VHC-Verlag AN - OPUS4-57826 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Meyer, A. T1 - About the Influence of (Non-)Solvents on the Ring Expansion Polymerization of l-Lactide and the Formation of Extended Ring Crystals N2 - Ring-expansion polymerizations (REPs) catalyzed by two cyclic tin catalysts (2-stanna-1.3-dioxa-4,5,6,7-dibenzazepine [SnBiph] and 2,2-dibutyl-2-stanna-1,3-dithiolane [DSTL]) are performed at 140 °C in bulk. Small amounts (4 vol%) of chlorobenzene or other solvents are added to facilitate transesterification reactions (ring–ring equilibration) in the solid poly(l-lactide)s. In the mass range up to m/z 13 000 crystalline PLAs displaying a so-called saw-tooth pattern in the MALDI-TOF mass spectra are obtained indicating the formation of extended-ring crystals. The characteristics of extended-ring crystallites and folded-ring crystallites are discussed. Furthermore, extremely high melting temperatures (Tm’s up to 201.2 °C) and melting enthalpies (𝚫Hm’s up to 106 J g−1)) are found confirming that 𝚫Hm max, the 𝚫Hm of a perfect crystal, is around or above 115 J g−1 in contrast to literature data. KW - Polylactide KW - MALDI-TOF MS KW - Ring-expansion polymerization KW - Biobased PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-573063 DO - https://doi.org/10.1002/macp.202200385 VL - 224 IS - 5 SP - 1 EP - 8 PB - Wiley VHC-Verlag AN - OPUS4-57306 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - About the crystallization of cyclic and linear poly(L-lactide)s in alcohol-initiated and Sn(II)2-ethylhexanoate- catalyzed ROPs of L-lactide conducted in solution N2 - 1-Hydroxymethylnaphtalene (HMN) or 11-bromoundecanol (BUND) were used as initiators and Sn(II) 2-ethylhexanoate (SnOct2) as catalyst for ROPs of L-Lactide (LA) at 115 °C in bulk or in 4 M and 2M solutions in toluene. The LA/In ratio, the LA/Cat ratio and the time were varied. The matrix-assisted laser desorption/ionization time-of-flight (MALDI TOF) mass spectra exclusively displayed peaks of linear chains, when the ROPs were conducted in bulk. But in contrast to reports in the literature, mixtures of linear and cyclic poly(L-lactide) (PLA), were obtained, when the ROPs were performed in solution. The intensity distribution of the mass peaks of cyclic PLAs displayed a “saw-tooth pattern” after annealing in contrast to the mass peak distribution of the liner chains. This new phenomenon indicated that cyclic PLAs and linear PLAs crystallized in separate crystals from the same reaction mixture. This conclusion was confirmed by fractionated crystallization from 2 M solution, which confirmed that the cyclic PLAs nucleate and crystallize faster than the linear chains. KW - Polylactide KW - MALDI-TOF MS KW - Ring opening polymerization KW - Crystallization PY - 2023 DO - https://doi.org/10.1016/j.polymer.2023.125946 SN - 0032-3861 VL - 276 SP - 1 EP - 11 PB - Elsevier Ltd. AN - OPUS4-57308 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Kricheldorf, H. R. T1 - Alcohol-initiated and Tin(II) 2-ethylhexanoate-catalyzed polymerization of L-lactide in bulk – About separate crystallization of cyclic and linear Poly (L-lactide)s N2 - Alcohol-initiated ROPs of L-Lactide were performed at 140 ◦C in bulk with variation of the initiator/catalyst ratio and time. Lower ratios favor the formation of cycles which upon annealing display a change of the MALDI mass peak distribution towards a new maximum with a “saw-tooth pattern” of the mass peaks representing the cycles. Such a pattern was not observed for the mass peak of the linear chains. The coexistence of these patterns indicate that linear and cyclic poly (L-lactide)s (PLA) crystallize in separate crystals, and that the crystallites of the cycles are made up by extended rings. High Tm and ΔHm values confirm that these extended-ring crystallites represent a thermodynamically optimized form of PLA. Experiments with preformed cyclic and linear PLAs support this interpretation. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity KW - Polymerization PY - 2023 DO - https://doi.org/10.1016/j.polymer.2023.126355 VL - 285 IS - 126355 SP - 1 EP - 9 PB - Elsevier Ltd. AN - OPUS4-58355 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen T1 - Cyclic and linear poly(L-lactide)s by ring-expansion polymerization with Bu2SnO, Oct2SnO, and Bu2SnS N2 - To elucidate the usefulness of commercial Bu2SnO as catalyst for syntheses of linear and/or cyclic polylactides L-Lactide was polymerized in bulk with variation of the LA/Cat ratio, temperature and time. Based on a ring-expansion polymerization (REP) mechanism cyclic polylactides (PLAs) with weight average molecular weights in the range of 200,000–300,000 are obtained at the highest temperature (180 °C). Polymerizations at 150 °C yielded crystalline, mainly cyclic polylactides which, after annealing, showed high melting temperatures (up to 197.5 °C) and high crystallinities (>80%). Polymerization at 120 °C confirmed the trend towards more linear chains with lower temperatures but yielded extended-ring crystals showing a “saw-tooth pattern” in the mass spectra. Oct2SnO gave similar results as Bu2SnO. Bu2SnS proved a sluggish polymerization catalyst, but a good transesterification catalyst in solid PLA. KW - MALDI TOF MS KW - Biobased polymers KW - Polylactide KW - Ring-expansion polymerization PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584121 DO - https://doi.org/10.1002/pol.20230515 SN - 2642-4169 SP - 1 EP - 10 PB - Wiley CY - Hoboken, NJ AN - OPUS4-58412 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Kricheldorf, H. T1 - Transformation of poly(L-lactide) crystals composed of linear chains into crystals composed of cycles N2 - A poly(L-lactide) with a trifluoroethyl ester end group and an average degree of polymerization (DP) of 50 was synthesized by ROP of L-lactide initiated with trifluoroethanol. Small-angle X-ray scattering (SAXS) in combination with differential scanning calorimetry (DSC) measurements revealed an average crystal thickness of 13 nm, corresponding to 45 repeat units. This suggests that most crystallites were formed by extended PLA chains, and both flat surfaces were covered by CF3 groups. The crystalline PLAs were annealed at 140 or 160 °C in the presence of two catalysts: tin(II) 2-ethylhexanoate, (SnOct2) or dibutyltin bis(pentafluorophenoxide) (BuSnPhF). The chemical reactions, such as polycondensation and cyclization, proceeded in the solid state and were monitored by matrix-assisted laser desorption/ionization time-offlight (MALDI TOF) mass spectrometry and gel permeation chromatography (GPC) measurements. Under optimal conditions a large fraction of linear chains was transformed into crystallites composed of extended cycles. Additionally, MALDI TOF MS analysis of GPC fractions from samples annealed for 28 or 42 days detected chain elongation of the linear species up to a factor of 20. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity KW - Transesterification PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597250 DO - https://doi.org/10.1039/D3PY01370G SN - 1759-9954 VL - 15 IS - 12 SP - 1173 EP - 1181 PB - Royal Society for Chemistry AN - OPUS4-59725 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Meyer, A. A1 - Falkenhagen, Jana A1 - Kricheldorf, H. R. T1 - Polycondensations and Cyclization of Poly(L-lactide) Ethyl Esters in the Solid State N2 - The usefulness of seven different Tin catalysts, Bismuth subsalicylate and Titan tetra(ethoxide) for the polycondensation of ethyl L-lactate (ELA) was examined at 150 °C/6 d. Dibutyltin bis(phenoxides) proved to be particularly effective. Despite the low reactivity of ELA, weight average molecular masses (Mw) up to 12 500 were found along with partial crystallization. Furthermore, polylactides (PLAs) of similar molecular masses were prepared via ELA-initiated ROPs of L-lactide by means of the four most effective polycondensation catalysts. The crystalline linear PLAs were annealed at 140 or 160 °C in the presence of these catalysts. The consequences of the transesterification reactions in the solid PLAs were studied by means of matrix-assisted laser desorption/ionization (MALDI TOF) mass spectrometry, gel permeation chromatography (GPC) and small-angle X-ray scattering (SAXS). The results indicate that polycondensation and formation of cycles proceed in the solid state via formation of loops on the surface of the crystallites. In summary, five different transesterification reactions are required to explain all results. KW - Polylactide KW - MALDI-TOF MS KW - Crystalinity PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-592934 DO - https://doi.org/10.1039/d3py01232h SN - 1759-9962 VL - 15 IS - 2 SP - 71 EP - 82 PB - RSC Publ. CY - Cambridge AN - OPUS4-59293 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen T1 - Low Molar Mass Cyclic Poly(L-lactide)s: Separate Transesterification Reactions of Cycles and Linear Chains in the Solid State N2 - L-Lactide (LA) was polymerized with neat tin(II) 2-ethylhexanoate (SnOct2) in toluene at 115 °C at low concentration with variation of the LA/Cat ratio. Cyclic polylactides (cPLAs) with number average molecular weights (Mn) between 7 000 and 17 000 were obtained. MALDI-TOF mass spectrometry also revealed the formation of a few percent of linear chains. Crystalline cPLAs with Mn around 9 000 and 14 000 were annealed at 140 °C in the presence of ScOct2 or dibutyl-2-stanna-1,3-dithiolane (DSTL). Simultaneously, crystallites of extended linear chains and crystallites of extended cycles were formed regardless of the catalyst, indicating that transesterification reaction proceeded different for linear chains and for cycles, governed by thermodynamic control. The formation of extended chain crystallites with low dispersity indicates the existence of symproportionation of short and long chains. A complementary experiment was carried out with a PLA ethyl ester composed mainly of linear chains with a small fraction of cycles KW - Polylactide KW - MALDI-TOF MS KW - Annealing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-606228 DO - https://doi.org/10.1039/D4SM00567H SN - 1744-6848 SP - 1 EP - 12 PB - Royal Society of Chemistry (RSC) AN - OPUS4-60622 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gross, J.H. A1 - Weidner, Steffen T1 - Influence of Electric Field Strength and Emitter Temperature on Field Desorption Mass Spectra of Polyethylene Oligomers N2 - The influence of electric field strength and emitter temperature on dehydrogenation and C–C cleavage in field desorption (FD) mass spectrometry of polyethylene (PE) oligomers of average molecular weights ranging from 500 to 2000 is examined. Low mass oligomers yield molecular weight (MW) distributions that are basically in accordance with results from gel-permeation chromatography. For these materials, dehydrogenation can be greatly reduced by reduction of the emitter potential. Furthermore, the influence of emitter potential on MW distributions indicates the occurrence of field-induced C–C cleavages. Reliable MW distributions are more difficult to obtain from higher mass oligomers by FD-MS because of the need for higher field strength and higher emitter temperatures to effect their desorption/ionization. Experiments reveal that the application of FD-MS to PE oligomers is limited not only by field-induced but also by thermally-induced fragmentations. Even then, FD mass spectra contain valuable information on mass range and homogeneity of PE samples up to about m/z 3600. PY - 2000 DO - https://doi.org/10.1255/ejms.300 SN - 1469-0667 SN - 1356-1049 SN - 1365-0718 IS - 6 SP - 11 EP - 17 PB - IM Publications CY - Chichester AN - OPUS4-11098 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Wigant, L. A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Weidner, Steffen A1 - Kühn, Gerhard A1 - Geng, Sh. A1 - Erdmann, J. A1 - Gorsler, H.-V. T1 - Plasmavorbehandlungen von Polymeroberflächen T2 - 2. Freiberger Polymertag CY - Freiberg DA - 1995-05-30 PY - 1995 SP - 17 Seiten CY - Freiberg AN - OPUS4-7014 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Weidner, Steffen A1 - Geng, Sh. A1 - Wigant, L. A1 - Wöll, Ch. A1 - Erdmann, J. A1 - Gorsler, H.-V. T1 - Characterization of plasma-modified organic surfaces by electron spectroscopy, SEIRA, and MALDI-TOF-MS T2 - 6th European Conference on Applications of Surface and Interface Analysis CY - Montreux, Switzerland DA - 1995-10-09 PY - 1995 SP - TC 11 PB - Wiley CY - Chichester AN - OPUS4-7001 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Weidner, Steffen T1 - Copolyesters of lactide, isosorbide, and terephthalic acid-biobased, biodegradable, high-Tg engineering plastics N2 - Various copolyesters of lactide, isosorbide, and terephthalic acid are prepared by a two-step process performed in a 'one-pot' procedure, beginning with an isosorbide-initiated oligomerization of L-lactide followed by polycondensation with terephthaloyl chloride using SnCl2 as a catalyst for both steps. The SEC data show the formation of random copolyesters with high polydispersities as a consequence of the relatively high fraction of cyclics proved by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). The glass-transition temperatures (89–180 °C) obey an almost linear trend with the molar composition. The thermostability decreases with increasing lactide content. The successful incorporation of phenyl phosphate results in copolyesters of lower inflammability. KW - Biodegradability KW - Cyclization KW - Isosorbide KW - Polycondensation KW - Ring-opening polymerization PY - 2013 DO - https://doi.org/10.1002/macp.201200612 SN - 1022-1352 SN - 1521-3935 VL - 214 IS - 6 SP - 726 EP - 733 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-28171 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chatti, S. A1 - Weidner, Steffen A1 - Fildier, A. A1 - Kricheldorf, H.R. T1 - Copolyesters of isosorbide, succinic acid, and isophthalic acid: biodegradable, high Tg engineering plastics N2 - Isosorbide, succinyl chloride and isophthaloyl chloride are polycondensed under various reaction conditions. The heating in bulk with or without catalysts as well in an aromatic solvent without catalyst, and polycondensation with the addition of pyridine only yield low molar mass copolyesters. However, heating in chlorobenzene with addition of SnCl2 or ZnCl2 produces satisfactory molar masses. The number average molecular weights (Mn) of most copolyesters fall into the range of 7000–15,000 Da with polydispersities (PD) in the range of 3–9. The MALDI-TOF mass spectra almost exclusively displayed peaks of cyclics indicating that the chain growth was mainly limited by cyclization and not by side reactions, stoichiometric imbalance or incomplete conversion. The glass-transition temperatures increased with the content of isophthalic acid from 75 to 180 °C and the thermo-stabilities also followed this trend. KW - Biodegradable KW - Cyclization KW - Cyclopolymerization KW - Isophthalic acid KW - Isosorbide KW - Polycondensation KW - Polyesters KW - Renewable resources KW - Succinic acid PY - 2013 DO - https://doi.org/10.1002/pola.26635 SN - 0360-6376 SN - 0887-624X VL - 51 IS - 11 SP - 2464 EP - 2471 PB - Wiley CY - Hoboken, NJ AN - OPUS4-28577 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Weidner, Steffen A1 - Scheliga, F. A1 - Lahcini, M. T1 - Poly(epsilon-caprolactone) by combined ring-opening polymerization and polycondensation N2 - Numerous water-initiated polymerizations of εCL are conducted in bulk with variation of catalyst, reaction time, and temperature. The conversions are determined by 1H NMR and the molar masses by SEC measurements. For polymerizations at 100 °C, Bi triflate and Hf triflate are used as catalysts, whereas at 140 °C, Al triflate, Sn(II) triflate, SnCl2, HfCl4, BiCl3, and LaCl3 are used. In addition to a closed reaction vessel, experiments are also performed with stirring in a vacuum. Under these conditions, the best catalyst (SnCl2) yields 2–3 times higher molar masses and mass spectra indicate a significant higher fraction of cyclic polymers. The results prove that a modification of the procedure may stimulate a polycondesation process without change of catalyst, time, and temperature. KW - Epsilon-Caprolactone KW - Cyclization KW - MALDI-TOF mass spectrometry KW - Polycondensations KW - Ring-opening polymerizations PY - 2012 DO - https://doi.org/10.1002/macp.201200061 SN - 1022-1352 SN - 1521-3935 VL - 213 IS - 14 SP - 1482 EP - 1488 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-26273 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Weidner, Steffen T1 - High Tg copolyesters of lactide, isosorbide and isophthalic acid N2 - Using SnCl2, ZnCl2, Zn-lactate or Zr-acetylacetonate as catalysts ʟ-lactide was oligomerized in bulk with isosorbide as initiator. The ratio isosorbide/lactide was varied from 8/2 to 2/8. The resulting oligomers were in situ polycondensed with isophthaloyl chloride in various aromatic solvents. In chlorobenzene homogeneous reaction mixtures were obtained, whereas molten copolyesters precipitated from toluene and xylene. The obtained average molecular weights indicated high polydispersities. According to MALDI-TOF MS the low molar mass reaction products (<4 kDa) almost exclusively consisted of cyclics with a composition depending on the feed ratio. The glass-transition temperatures (Tg) varied between the values of poly(ʟ-lactide (64 °C) and poly(isosorbide isophthalate) (180 °C). Four polyesters prepared from 5-tert-butyl isophthalic acid displayed higher Tg values. Differential thermoanalysis evidenced that the thermostability decreases with higher fractions of lactide, but processing from the melt seems to be feasible up to temperatures of 260 °C without risking degradation. KW - Lactide KW - Isosorbide KW - Ring-opening polymerization KW - Polycondensation KW - Cyclization PY - 2013 DO - https://doi.org/10.1016/j.eurpolymj.2013.05.007 SN - 0014-3057 SN - 1873-1945 VL - 49 IS - 8 SP - 2293 EP - 2302 PB - Elsevier CY - Oxford AN - OPUS4-29014 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Scheliga, F. A1 - Kricheldorf, H.R. T1 - Low-temperature polymerization of epsilon-caprolactone catalyzed by cerium triflates N2 - Using 22 metal triflates as catalysts, ε-caprolactone is polymerized at 22 °C in bulk. Only five relatively acidic triflates prove active. Three triflates, including the neutral Sm3+, are active using water as initiator. A very low content of cyclics is found in all the experiments. With Ce3+ and Ce4+, polymerizations are performed in CH2Cl2 and in bulk at 2 °C and 22 °C. Low dispersities (down to 1.1) are obtained. At 22 °C, Ce4+ and, even better, Ce3+ also catalyze syntheses of CO2H- and CH2OH-terminated polycaprolactones, whereby higher dispersities and larger fractions of cyclics are obtained. Further polymerizations and polycondensations are catalyzed with protic acids. The results can be explained by a proton-catalyzed activated monomer mechanism. KW - Epsilon-caprolactone KW - Cyclization KW - Metal triflates KW - Polycondensation KW - Ring-opening polymerization PY - 2013 DO - https://doi.org/10.1002/macp.201300279 SN - 1022-1352 SN - 1521-3935 VL - 214 IS - 18 SP - 2043 EP - 2053 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-29219 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Garaleh, M. A1 - Lahcini, M. A1 - Kricheldorf, H.R. A1 - Weidner, Steffen T1 - Syntheses of aliphatic polyesters catalyzed by lanthanide triflates N2 - Polycondensations of 1,6-hexane diol and sebacic acid were conducted in bulk with addition of a lanthanide triflate as acidic catalyst. With exception of promethium triflate all lanthanide triflates were studied. A particularly low molecular weight was obtained with neodym triflate and the best results with samarium triflate. With Sm(OTf)3 weight average (Mw) values up to 65 kDa (uncorrected SEC data) were achieved after optimization of the reaction conditions. Comparison of these results with those obtained from bismuth, magnesium, and zinc triflates, on the one hand, and comparison with the acidities of all catalysts, on the other, indicates that the esterification mechanism involves complexation of monomer by metal ions. Preparation of multiblock copoly(ether ester)s failed due to insufficient incorporation of poly(tetrahydrofuran) diols. KW - Biodegradable polyesters KW - Lanthanide ions KW - Macrocycles KW - MALDI-TOF KW - Polycondensation PY - 2009 DO - https://doi.org/10.1002/pola.23136 SN - 0360-6376 SN - 0887-624X VL - 47 IS - 1 SP - 170 EP - 177 PB - Wiley CY - Hoboken, NJ AN - OPUS4-19626 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Yashiro, T. A1 - Weidner, Steffen T1 - Isomerization-free polycondensations of maleic anhydride with alpha,omega-alkanediols KW - Polymerisation KW - Polykondensation KW - MALDI Massenspektrometrie PY - 2009 DO - https://doi.org/10.1021/ma9009356 SN - 0024-9297 SN - 1520-5835 VL - 42 IS - 17 SP - 6433 EP - 6439 PB - American Chemical Society CY - Washington, DC AN - OPUS4-20930 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Poly(Epsilon-caprolactone) by combined ring-opening polymerization and azeotropic polycondensation - the role of cyclization and equilibration N2 - Using three different catalysts, water-initiated polymerizations of ε-caprolactone were conducted in bulk with variation of the monomer/water ratio. The resulting CH2OH and CO2H- terminated polylactones were subjected in situ to azeotropic polycondensations. With Bi-triflate and temperatures, the polycondensations were not much successful and involved side reactions. With ZnCl2, and especially SnCl2, considerably higher molar masses were achieved. The substitution of toluene for chlorobenzene for refluxing gave better results. The polycondensations broadened the molar mass distribution of the ROP-based prepolymers, and polydispersities between 1.4–1.8 were obtained. The MALDI–TOF mass spectra revealed that the polycondensations significantly enhanced the fraction of rings due to efficient 'end-biting' reactions. By comparison with copolymerization experiments and Sn methoxide-initiated polymerizations, it was demonstrated that equilibration reactions, such as the formation of rings by 'back-biting,' did not occur. KW - Ring-opening polymerization KW - Epsilon-caprolactone (e-CL) KW - Cyclization KW - MALDI-TOF mass spectrometry KW - Polycondensation KW - Polyesters PY - 2012 DO - https://doi.org/10.1002/pola.26222 SN - 0360-6376 SN - 0887-624X VL - 50 IS - 20 SP - 4206 EP - 4214 PB - Wiley CY - Hoboken, NJ AN - OPUS4-26500 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Mix, Renate A1 - Weidner, Steffen T1 - Poly(ester urethane)s derived from lactide, isosorbide, terephthalic acidm abd various diisocyanates N2 - Isosorbide-initiated oligomerizations of ʟ-lactide were preformed in bulk using SnCl2 as catalyst. The resulting telechelic OH-terminated oligoesters were in situ subjected to simultaneous polycondensation and polyaddition with mixtures of terephthaloyl chloride and diisocyanates. Most polymerizations were conducted with 4,4'-diisocyanatodiphenyl methane and 2,4-diisocyanato toluene. The consequences of excess diisocyanate and four different catalysts were studied. The isosorbide/lactide ratio and the terephthalic acid/diisocyanate ratio were varied. Number average molecular weights up to 15 kDa with polydispersities around 3–5 were obtained. Depending on the chemical structure of the copolyester and on the feed ratio, incorporation of urethane groups may reduce or enhance the glass-transition temperature, but the thermal stability decreases dramatically regardless of composition. KW - Cyclization KW - Isosorbide KW - Lactide KW - Polyaddition KW - Polycondensation KW - Polyesters KW - Polyurethanes PY - 2014 DO - https://doi.org/10.1002/pola.27069 SN - 0360-6376 SN - 0887-624X VL - 52 IS - 6 SP - 867 EP - 875 PB - Wiley CY - Hoboken, NJ AN - OPUS4-30299 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Garaleh, M. A1 - Kricheldorf, H.R. A1 - Weidner, Steffen A1 - Yashiro, T. T1 - Hafnium chloride catalyzed polycondensation of Alpha, Omega-alkanediol with dicarboxylic acids or succinic anhydride KW - Polyester KW - Polycondensation KW - Hafnium KW - Cyclization PY - 2010 DO - https://doi.org/10.1080/10601320903539199 SN - 1060-1325 SN - 1520-5738 VL - 47 IS - 4 SP - 303 EP - 308 PB - Taylor & Francis CY - Philadelphia, PA AN - OPUS4-22953 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kricheldorf, H.R. A1 - Scheliga, F. T1 - Cyclization and dispersity of poly(alkylene isophthalate)s N2 - Poly(alkylene isophthalate)s were prepared by different methods, either in solution or in bulk. The SEC measurements were evaluated in such a way that all oligomers were included. In solution (monomer conc. 0.1–0.7 mol/L) large fractions of rings were formed and high dispersities (up to 12) were obtained, which disagree with theoretical predictions. Polycondensations in bulk did neither generate cyclics by 'back-biting' nor by end-to-end cyclization, when the maximum temperature was limited to 210 °C. The dispersities of these perfectly linear polyesters were again higher than the theoretical values. Regardless of the synthetic method monomeric cycles were never observed. Furthermore, SEC measurements performed in tetrahydrofuran and in chloroform and SEC measurements performed in three different institutes were compared. Finally, SEC measurements of five samples were performed with universal calibration and a correction factor of 0.71 ± 0.02 was found for normal calibration with polystyrene. KW - Cyclization KW - Polycondensation KW - Polyesters KW - Size exclusion chromatography KW - Cyclics KW - Dispersity KW - SEC KW - Universal calibration KW - MALDI mass spectrometry PY - 2016 DO - https://doi.org/10.1002/pola.27892 SN - 0360-6376 SN - 0887-624X VL - 54 IS - 1 SP - 197 EP - 208 PB - Wiley CY - Hoboken, NJ AN - OPUS4-33731 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H.R. A1 - Weidner, Steffen A1 - Lahcini, M. T1 - Multicyclic polyesters of trimesic acid and alkanediols and the theory of network formation N2 - Trimesoyl chloride is polycondensed with various alpha,omega'-alkanediols in dichloromethane at different concentrations using equifunctional feed ratios. As evidenced by MALDI-TOF (matrix assisted laser desorption/ionization-time of flight) mass spectrometry the soluble reaction products mainly consist of perfect multicyclic oligomers and polymers. The solphase extracted from the gels also consists of perfect multicycles. SEC (size exclusion chromatography) measurements show that both soluble reaction products and extracted solphases also contain a high molar mass fraction of perfect and nonperfect multicycles extending up to masses beyond 10 5 g mol-1. When the polycondensation is stopped after a few minutes perfect multicycles are already detectable in the reaction mixture along with functional (multi)cyclic oligomers. These results prove that at initial monomer concentrations < 0.2 mol L-1 networks and large multicyclic polymers are synthesized from functional cyclic oligomers formed in early stages of the polycondensation and not from hyperbranched polymers. This interpretation is presented as 'egg-first theory' and compared with the 'hen-first theory' of Stockmayer and Flory. KW - a2 + b3 polycondensation KW - Cyclization KW - MALDI KW - Multicyclic polymers KW - Networks PY - 2015 DO - https://doi.org/10.1002/macp.201500245 SN - 1022-1352 SN - 1521-3935 VL - 216 IS - 21 SP - 2095 EP - 2106 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-35282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -