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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-508509 SP - 2000152 PB - Wiley AN - OPUS4-50850 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 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-507477 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. 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: Me2SnCl2