62876 2025 eng 2843 2857 6 33 article Springer Science and Business Media LLC New York, NY 1 -- -- -- Water-initiated ring-opening polymerizations (ROPs) of L-lactide (LA) were performed in bulk at 140 °C, whereupon 11 different salts or complexes of low-toxic metal ions such as tin (II), Zn(II), Zr(IV), and Bi(III) were used as catalysts. Only four catalysts gave satisfactory results despite a long reaction time (24 h). The influence of the temperature was studied with tin (II) 2-ethylhexanoate (SnOct2), dibutyltin oxide (Bu2SnO), and zinc bis-acetylacetonate (Zn(acac)2) and zirconium acetylacetonate (Zr(acac)4). With SnOct2, Bu2SnO and Zr(acac)4 the time was varied at 140 °C to compare their reactivity. Furthermore, two series of ROPs were carried out with variation of the LA/H2O ratio to verify the control of the molecular weight by the monomer-initiator ratio. Bi- or tri-modal molecular weight distributions (MWD) were found for most of the ROPs and bimodal melting endotherms in the differential scanning calorimetry (DSC) heating traces. The thickness and dependence of the 3D packing of the crystallites were monitored by small-angle X-ray scattering (SAXS) measurements. Journal of Polymers and the Environment 10.1007/s10924-025-03565-w urn:nbn:de:kobv:b43-628761 1572-8919 true {"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,4,5]],"date-time":"2025-04-05T22:40:08Z","timestamp":1743892808225,"version":"3.40.3"},"reference-count":40,"publisher":"Springer Science and Business Media LLC","license":[{"start":{"date-parts":[[2025,4,5]],"date-time":"2025-04-05T00:00:00Z","timestamp":1743811200000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2025,4,5]],"date-time":"2025-04-05T00:00:00Z","timestamp":1743811200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"}],"funder":[{"DOI":"10.13039\/501100005711","name":"Universit\u00e4t Hamburg","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100005711","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":["link.springer.com"],"crossmark-restriction":false},"short-container-title":["J Polym Environ"],"abstract":"<jats:title>Abstract<\/jats:title>\n <jats:p>Water-initiated ring-opening polymerizations (ROPs) of L-lactide (LA) were performed in bulk at 140\u00a0\u00b0C, whereupon 11 different salts or complexes of low-toxic metal ions such as tin (II), Zn(II), Zr(IV), and Bi(III) were used as catalysts. Only four catalysts gave satisfactory results despite a long reaction time (24\u00a0h). The influence of the temperature was studied with tin (II) 2-ethylhexanoate (SnOct<jats:sub>2<\/jats:sub>), dibutyltin oxide (Bu<jats:sub>2<\/jats:sub>SnO), and zinc bis-acetylacetonate (Zn(acac)<jats:sub>2<\/jats:sub>) and zirconium acetylacetonate (Zr(acac)<jats:sub>4<\/jats:sub>). With SnOct<jats:sub>2,<\/jats:sub> Bu<jats:sub>2<\/jats:sub>SnO and Zr(acac)<jats:sub>4<\/jats:sub> the time was varied at 140\u00a0\u00b0C to compare their reactivity. Furthermore, two series of ROPs were carried out with variation of the LA\/H<jats:sub>2<\/jats:sub>O ratio to verify the control of the molecular weight by the monomer-initiator ratio. Bi- or tri-modal molecular weight distributions (MWD) were found for most of the ROPs and bimodal melting endotherms in the differential scanning calorimetry (DSC) heating traces. The thickness and dependence of the 3D packing of the crystallites were monitored by small-angle X-ray scattering (SAXS) measurements.<\/jats:p>","DOI":"10.1007\/s10924-025-03565-w","type":"journal-article","created":{"date-parts":[[2025,4,5]],"date-time":"2025-04-05T22:25:37Z","timestamp":1743891937000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["H2O-Initiated Polymerization of L-Lactide"],"prefix":"10.1007","author":[{"given":"Hans R.","family":"Kricheldorf","sequence":"first","affiliation":[]},{"given":"Steffen M.","family":"Weidner","sequence":"additional","affiliation":[]}],"member":"297","published-online":{"date-parts":[[2025,4,5]]},"reference":[{"issue":"8","key":"3565_CR1","doi-asserted-by":"crossref","first-page":"820","DOI":"10.1016\/j.progpolymsci.2008.05.004","volume":"33","author":"L-T Lim","year":"2008","unstructured":"Lim L-T, Auras R, Rubino M (2008) Processing technologies for Poly (lactic acid). 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Kricheldorf Steffen Weidner eng uncontrolled MALDI-TOF MS eng uncontrolled Polylactide eng uncontrolled Ring-opening polymerization eng uncontrolled Crystallization Analytische Chemie 6 Materialchemie 6.3 Strukturanalytik Chemie und Prozesstechnik Chemische Charakterisierung und Spurenanalytik Verlagsliteratur Datei für die Öffentlichkeit verfügbar ("Open Access") Wissenschaftliche Artikel der BAM Bundesanstalt für Materialforschung und -prüfung (BAM) https://opus4.kobv.de/opus4-bam/files/62876/s10924-025-03565-w.pdf