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 U6 - 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 U6 - 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 U6 - 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 U6 - 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 U6 - 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 - 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 U6 - 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 - 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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-543066 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 - 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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-557565 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 - 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 U6 - 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 U6 - 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 U6 - 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, Hans A1 - Weidner, Steffen T1 - High molar mass cyclic poly(L-lactide) via ring-expansion polymerizationwith cyclic dibutyltin bisphenoxides N2 - Two new catalysts (SnNa and SnBi) were prepared from dibutyltin oxide and 2,2′-dihydroxybiphenyl or2,2′dihydroxy(1,1′-binaphtyl). These catalysts enabled rapid polymerizations of L-lactide at 160 or 180 °C in bulk, whereby almost exclusively cyclic polylactides were formed. These polymerizations were free of racemization and yielded pol(L-lactide)s having weight average molecular weights (Mw's) up to 140 000 g mol−1. The Mw's varied little with the Lac/Cat ratio as expected for a ring expansion polymerization (REP). Polymerizations performed in bulk at 140, 120 and 102 °C yielded cyclic polylactides with lower molecular weights. At 102 °C a strong predominance of even-numbered cycles was found with SnNa as catalyst. SnNa can also catalyze alcohol-initiated ROPs yielding linear poly(L-lactide) free of cyclics. KW - MALDI-TOF MS KW - Polylactide KW - Ring-opening Polymerization KW - Cyclization KW - Catalysts PY - 2018 U6 - https://doi.org/10.1016/j.eurpolymj.2018.05.036 SN - 0014-3057 SN - 1873-1945 VL - 105 SP - 158 EP - 166 PB - Elsevier Ltd. AN - OPUS4-45439 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 U6 - 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 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 U6 - 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 - 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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-506419 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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-506458 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 U6 - 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, Hans A1 - Weidner, Steffen T1 - About the influence of salicylic acid on tin(II)octanoate-catalyzed ring opening polymerizationof L-lactide 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 U6 - 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 - 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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-488622 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. 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 U6 - 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 U6 - 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 U6 - 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 U6 - 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, Hans A1 - Weidner, Steffen A1 - Scheliga, Felix T1 - Ring-Expansion Polymerization (REP) of L-lactide with cyclic Tin(II) Bisphenoxides N2 - Five new cyclic catalysts were prepared by a new synthetic method from tin(II)-2-ethyhexanoate and silylated catechols, silylated 2,2´dihydroxybiphenyl or silylated 1,1´-bisnaphthol. These catalysts were compared with regard to their usefulness as catalysts for the ring expansion polymerization (REP) of L-lactide in bulk at 160 °C, and with two different tin(IV) derivatives of 1,1´binaphthol. Best results were obtained using seven-membered cyclic tin(II)bisphenoxides, which yielded colorless cyclic poly(l-lactide)s free of racemization with weight average molecular weights (Mw) up to 305 000 g mol-1. Furthermore, these catalysts were active even at a lactide/catalyst ratio of 20 000/1. Our new results were superior to those obtained from all other previously published catalysts yielding cyclic poly(L-lactide). The seven-membered cycles also proved to be more active than tin(II) 2-ethylhexanoate with and without the addition of alcohol. KW - Lactide KW - Cyclization KW - Ring-expansion polymerization KW - Tin(II)octanoate KW - MALDI-TOF MS PY - 2019 U6 - https://doi.org/10.1016/j.eurpolymj.2019.04.024 SN - 0014-3057 SN - 1873-1945 VL - 116 SP - 256 EP - 264 PB - Elsevier Ltd. AN - OPUS4-47794 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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-596856 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 -