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- 2024 (2) (entfernen)
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- Annealing (1)
- Crystalinity (1)
- MALDI TOF MS (1)
- MALDI-TOF MS (1)
- Polyglycolide (1)
- Polylactide (1)
Organisationseinheit der BAM
- 6 Materialchemie (2)
- 6.3 Strukturanalytik (2)
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.
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