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 JF - Journal of Polymer Science A: Polymer Chemistry 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, Hans A1 - Weidner, Steffen T1 - About the influence of salicylic acid on tin(II)octanoate-catalyzed ring opening polymerizationof L-lactide JF - European Polymer Journal N2 - L-Lactide was polymerized in bulk with tin(II)2-ethylhexanoate SnOct2) as catalyst and salicylic acid as cocatalyst. The Lac/Cat ratio, Cocat/Cat ratio, temperature and time were varied. Increasing Cocat/Cat ratios reduced both,polymerization rate and molecular weight. However,under optimized conditions high molar mass (Mw up to 178,000), colorless, cyclic polylactides were formed in a short time. A few polymerizations performed at 160 and 180°C with the combination of SnOct2 and silylated salicylic acid gave similar results. Neat tin II) salicylate was prepared from SnOct2 and used for REPs of L-lactide in bulk, but the results were not better than those obtained from combinations of SnOct2 and salicylic acid. Furthermore, dibutyltin salicylate was synthesized and used as catalyst for polymerizations of L-lactide in bulk at temperatures varying from 102 to 160°C. Cyclic polylactides with Mw’s up to 40,000 were the main reaction products. At 100–102°C a predominance of odd-numbered cycles was found proving a REP mechanism. KW - Polylactide KW - MALDI-TOF MS KW - Cyclization KW - Catalyst KW - Ring-opening polymerization PY - 2019 DO - https://doi.org/10.1016/j.eurpolymj.2019.07.003 VL - 119 SP - 37 EP - 44 PB - Elsevier Ltd. AN - OPUS4-49211 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 JF - Journal of polymer science A, polymer chemistry 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 T1 - Copolyesters of lactide, isosorbide, and terephthalic acid-biobased, biodegradable, high-Tg engineering plastics JF - Macromolecular chemistry and physics 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 - Kricheldorf, H. R. A1 - Weidner, Steffen T1 - Cyclic poly(L-lactide)s via simultaneous ROP and polycondensation (ROPPOC) catalyzed by dibutyltin phenoxides JF - European Polymer Journal 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 - Kricheldorf, H. A1 - Weidner, Steffen A1 - Scheliga, F. T1 - Cyclic poly(lactide)s via the ROPPOC method catalyzed by alkyl- or aryltin chlorides JF - Journal of Polymer Science, Polymer Chemistry 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. A1 - Weidner, Steffen A1 - Meyer, A. T1 - Syntheses of Polyglycolide via Polycondensation: A Reinvestigation JF - Macromolecular Chemistry and Physics 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 - 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 JF - Journal of Polymer Science A-Polymer Chemistry 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 A1 - Scheliga, F. T1 - Synthesis of cyclic polymers and flaws of the Jacobson–Stockmayer theory JF - RSC Polymer Chemistry 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 - Kricheldorf, H. T1 - Transesterification in alcohol-initiated ROPs of l- and meso-lactide catalyzed by Sn(II) and Sn(IV) compounds at low temperatures JF - Macromolecular Chemistry and Physics 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 -