TY - CONF
A1 - Weidner, Steffen
T1 - MALDI-ToF mass spectrometry for the characterization of biobased polymers suitable for depollution
N2 - In this work, bio-based polymers were synthesized and designed as polymers phases for adsorption of a variety of pollutants from aqueous solutions. The obtained adsorption results showed that the integration of bio-sourced synthons generate attractive hydrophilicity, and wettability of the resulting adsorbent phase. Such polymers phases enable stronger interactions with the organic and inorganic pollutants in water.
A wide variety of different bio-based polymers structures (e. g. poly(ethersulfones, poly(etherphosphines or poly(etherpyridines) with different functional groups were successfully designed in order to adapt chemical structure to different pollutants type and matrice nature.
In order to characterize and to determine the correlation between polymer structures and nature of interaction with pollutants, different analytical technics (NMR, GPC, ATG, DSC, Mass spectrometry) were successfully used. Amongst them, MALDI TOF mass spectrometry plays a superior role since this technique enables the simultaneous determination of the polymer structure, polymer end groups and molecular weight.
This work focusses on the characterization of synthesized polymers. The chemical structure of the repeating unit, the nature of the end groups, as well as the molecular weight, which are all important for the specific interactions of the polymer with the pollutants were clearly determined and suggestions to improve these interactions by changing the synthetic pathway could be given.
T2 - 12. Journees maghreb-europe. Matériaux et Applications aux Dispositifs et Capteurs
CY - Monastir, Tunisia
DA - 08.11.2022
KW - MALDI TOF MS
KW - Biobased polymers
KW - Depollution
PY - 2022
AN - OPUS4-56237
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Weidner, Steffen
T1 - MALDI Mass spectrometry of synthetic polymers – making molecular elephants to fly
N2 - The importance of MALDI TOF mass spectrometry for the analysis of synthetic polymers is shown and some specific issues influencing the analysis e.g. polymer mass dispersity, matrix and matrix homogeneity, nature of cations and end groups, sequence distribution are discussed by means of examples.
T2 - Merck Polymer Seminar
CY - Online meeting
DA - 29.04.2021
KW - MALDI-ToF MS
KW - Ionization
KW - Desorption
KW - Polymers
PY - 2021
AN - OPUS4-52545
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Weidner, Steffen
T1 - MALDI-TOF MS in der Synthese hochmolekularer Polylaktid Homo- und Copolymere
N2 - Die MALDI-TOF Massenspektrometrie stellt eine wichtige Methode zur simultanen Bestimmung von Molmassen, Molmassenverteilungen und Endgruppen von synthetischen Polymeren dar. In dem Vortrag wird gezeigt, welche zusätzlichen Informationen über die Art der Polymerisation, der Nebenreaktionen und der Topologie der gebildeten hochmolekularen Polylaktid-Homo- und Copolymere im Verlauf ihrer Synthese erhalten werden können.
T2 - Bruker Anwendertreffen
CY - Online meeting
DA - 05.03.2021
KW - MALDI
KW - Polylaktide
PY - 2021
AN - OPUS4-52278
LA - deu
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 - CONF
A1 - Weidner, Steffen
T1 - Differences in MALDI Ionization of neat linear and cyclic poly(L-lactide)s
N2 - In addition to molar mass distribution (MMD) synthetic polymers often exhibit an additional chemical heterogeneity distribution, expressed by different end groups and other structural variations (e.g. tacticity, copolymer composition etc.). Ionization in MALDI MS is always strongly affected by such chemical properties. For example, the abundance of cyclics in MALDI TOF mass spectra is frequently reported to greatly exceed that of linears. Thus, the MALDI ionization behavior of various neat end-capped linear poly(L-lactide)s and one cyclic poly(L-lactide) was investigated and compared with that of blends of both structures. Moreover, the influence of the cationizing salt was investigated too.
Neat compounds and various blends of cyclic and linear species were prepared and studied using two MALDI TOF mass spectrometers under identical conditions with regard to sample preparation and instrumental conditions, except for the laser power and the salt used for cationization. Polymer samples were additionally characterized by NMR and SEC.
The steady increase of the laser intensity caused an exponential increase of the peak intensities of both linear and cyclic polylactides.The response of linear polylactides (in the investigated molecular mass range), whether as neat polymer or in blends with other linear polylactides was almost similar. This clearly supports our assumption that ionization in MALDI is probably unaffected by the end group structure.The variation of the laser power shows only little effect on the intensity ratio of linear-to linear and cyclic-to-linear polylactides in blends. Whereas neat linear polylactides at all laser intensities have a significantly higher abundance than neat cyclics, in mixtures of both an overestimation of cyclic species in MALDI TOF mass spectra of polylactides was found. However, this is far less distinct than frequently reported for other polymers.Concluding, peak suppression of linear polymers in mixtures of both architectures can be excluded, which also means, that polylactides showing only peaks of cyclic compounds in their MALDI - TOF mass spectra do not contain a significant fraction of linear analogues.
Our study is the first systematic comparison of the MALDI ionization of neat and blended cyclic and linear polylactides.
T2 - ASMS 2020 Reboot
CY - Online meeting
DA - 01.06.2020
KW - MALDI
KW - Ionization
KW - Linear
KW - Cyclic
KW - Polylactide
PY - 2020
AN - OPUS4-50852
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Meyer, Andreas
A1 - Weidner, Steffen
A1 - Kricheldorf, Hans R.
T1 - Star-shaped poly(l-lactide)s based on pentaerythritol: About crystallization and polycondensation plus disproportionation and ring formation in the solid state
N2 - Star-shaped poly( L-lactide)s (s-PLAs), were prepared by ring-opening polymerization of with pentaerythritol and catalyzed by tin(II) 2-ethylhyexanoate (SnOct out in bulk at either 120 ◦ C or 160 ◦ L-lactide (LA) initiated 2 ). Two small series of ROPs were carried C with variation of the LA/initiator ratio. Matrix-assisted laser desorption/ ionization time-of-flight (MALDI-TOF) mass spectra revealed traces of cycles in 120 ◦ C samples only at low initiator/catalyst ratios. In contrast, higher fractions of cycles were detected in samples prepared at 160 C, suggesting a "back-biting" origin. The influence of arm length and thermal history on crystallinity was investigated by differential scanning calorimetry (DSC) and wide-angle x-ray scattering (WAXS). It was shown that annealing increased the melting temperature (T ◦ ◦ m ) and crystallinity. However, annealing at 140 ◦ C for 14 d also caused significant solid-state transesterification. In addition, crystallites composed of s-PLAs with extended arms and, simultaneously, crystallites composed exclusively of extended rings were formed, identified by their typical "sawtooth" pattern in the MALDI mass spectra. Small angle x-ray scattering (SAXS) indicated that the crystal thickness was lower than that of linear PLAs annealed under identical conditions, but increased upon annealing at 140 C.
KW - MALDI-TOF MS
KW - Polylactide
KW - Crystallisation
KW - AStar-shaped polymers
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-636832
DO - https://doi.org/10.1016/j.polymer.2025.128709
SN - 0032-3861
VL - 334
SP - 1
EP - 11
PB - Elsevier Ltd.
AN - OPUS4-63683
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rösler, Alexander
A1 - Weidner, Steffen
A1 - Klamroth, Tillmann
A1 - Müller, Axel HE
A1 - Schlaad, Helmut
T1 - Kinetics of anionic polymerization of β‐myrcene in hydrocarbon solvents
N2 - AbstractThe kinetics of anionic polymerization of β‐myrcene initiated by sec‐butyllithium were examined in saturated and unsaturated hydrocarbon solvents, i.e. cyclohexane, cyclohexene, 4‐vinylcyclohexene and dl‐limonene. Polymerizations usually proceeded in a living manner, i.e. in the absence of termination and chain transfer reactions, in all solvents, to produce well‐defined polymyrcenes with high content (85%) of cis‐1,4 units. However, polymyrcenyllithium chains exhibited limited long‐term stability in 4‐vinylcyclohexene solution, most probably due to chain transfer to solvent. Reaction orders with respect to the concentration of active chains were found to be one‐quarter in cyclohexane increasing to one‐half in unsaturated solvents, indicating that the polymyrcenyllithium chains are present as tetrameric or dimeric associates, respectively. Apparent activation energies were found to be 81 kJ mol−1 in cyclohexane and 77 kJ mol−1 in dl‐limonene solution, which are close to the values obtained by quantum chemical calculations. © 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
KW - Myrcene
KW - Anionic polymerization
KW - Reaction order
KW - Activation energy
KW - Microstructure
KW - Quantum chemical calculation
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-636840
DO - https://doi.org/10.1002/pi.6772
SN - 0959-8103
SP - 1
EP - 8
PB - Wiley
AN - OPUS4-63684
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rösler, Alexander
A1 - Weidner, Steffen
A1 - Klamroth, Tillmann
A1 - Müller, Axel HE
A1 - Schlaad, Helmut
T1 - Kinetics of anionic polymerization of β‐myrcene in hydrocarbon solvents
N2 - AbstractThe kinetics of anionic polymerization of β‐myrcene initiated by sec‐butyllithium were examined in saturated and unsaturated hydrocarbon solvents, i.e. cyclohexane, cyclohexene, 4‐vinylcyclohexene and dl‐limonene. Polymerizations usually proceeded in a living manner, i.e. in the absence of termination and chain transfer reactions, in all solvents, to produce well‐defined polymyrcenes with high content (85%) of cis‐1,4 units. However, polymyrcenyllithium chains exhibited limited long‐term stability in 4‐vinylcyclohexene solution, most probably due to chain transfer to solvent. Reaction orders with respect to the concentration of active chains were found to be one‐quarter in cyclohexane increasing to one‐half in unsaturated solvents, indicating that the polymyrcenyllithium chains are present as tetrameric or dimeric associates, respectively. Apparent activation energies were found to be 81 kJ mol−1 in cyclohexane and 77 kJ mol−1 in dl‐limonene solution, which are close to the values obtained by quantum chemical calculations. © 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
KW - Myrcene
KW - Anionic polymerization
KW - MALDI TOF MS
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-649039
DO - https://doi.org/10.1002/pi.6772
SN - 0959-8103
SP - 1
EP - 8
PB - Wiley
AN - OPUS4-64903
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 - 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 -