{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,26]],"date-time":"2026-01-26T10:55:08Z","timestamp":1769424908910,"version":"3.49.0"},"reference-count":36,"publisher":"MDPI AG","issue":"10","license":[{"start":{"date-parts":[[2022,10,20]],"date-time":"2022-10-20T00:00:00Z","timestamp":1666224000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Initiatives for Science, Innovation, Territories and Economy (I-SITE) Lille Nord\u2014Europe"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Catalysts"],"abstract":"<jats:p>Organocatalysts for polymerization have known a huge interest over the last two decades. Among them, heterocyclic nitrogen bases are widely used to catalyse the ring-opening polymerization (ROP) of heterocycles such as cyclic carbonates. We have investigated the ring-opening polymerization of trimethylene carbonate (TMC) catalysed by DMAP (4-dimethylaminopyridine) and TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) as case studies in the presence of methanol as co-initiator by Density Functional Theory (DFT). A dual mechanism based on H-bond activation of the carbonyl moieties of the monomer and a basic activation of the alcohol co-initiator has been shown to occur more preferentially than a direct nucleophilic attack of the carbonate monomer by the heterocyclic nitrogen catalyst. The rate-determining step of the mechanism is the ring opening of the TMC molecule, which is slightly higher than the nucleophilic attack of the TMC carbonyl by the activated alcohol. The calculations also indicate TBD as a more efficient catalyst than DMAP. The higher energy barrier found for DMAP vs. TBD, 23.7 vs. 11.3 kcal\u00b7mol\u22121, is corroborated experimentally showing a higher reactivity for the latter.<\/jats:p>","DOI":"10.3390\/catal12101280","type":"journal-article","created":{"date-parts":[[2022,10,20]],"date-time":"2022-10-20T20:35:55Z","timestamp":1666298155000},"page":"1280","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["DFT Investigations on the Ring-Opening Polymerization of Trimethylene Carbonate Catalysed by Heterocyclic Nitrogen Bases"],"prefix":"10.3390","volume":"12","author":[{"given":"Michael","family":"Lalanne-Tisn\u00e9","sequence":"first","affiliation":[{"name":"Sustainable Materials Lab, Department of Chemical Engineering, KU Leuven, Campus Kulak Kortrijk, Etienne Sabbelaan 53, Box 7659, B-8500 Kortrijk, Belgium"},{"name":"Universit\u00e9 de Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181\u2014UCCS\u2014Unit\u00e9 de Catalyse et Chimie du Solide, F-59000 Lille, France"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8510-9608","authenticated-orcid":false,"given":"Audrey","family":"Favrelle-Huret","sequence":"additional","affiliation":[{"name":"Universit\u00e9 de Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181\u2014UCCS\u2014Unit\u00e9 de Catalyse et Chimie du Solide, F-59000 Lille, France"}]},{"given":"Wim","family":"Thielemans","sequence":"additional","affiliation":[{"name":"Sustainable Materials Lab, Department of Chemical Engineering, KU Leuven, Campus Kulak Kortrijk, Etienne Sabbelaan 53, Box 7659, B-8500 Kortrijk, Belgium"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4419-6431","authenticated-orcid":false,"given":"Jo\u00e3o P.","family":"Prates Ramalho","sequence":"additional","affiliation":[{"name":"Chemistry Department, LAQV-REQUIMTE and Hercules Centre, Sciences and Technology School, University of \u00c9vora, Rua Rom\u00e3o Ramalho 59, 7000-671 \u00c9vora, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2329-9116","authenticated-orcid":false,"given":"Philippe","family":"Zinck","sequence":"additional","affiliation":[{"name":"Universit\u00e9 de Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181\u2014UCCS\u2014Unit\u00e9 de Catalyse et Chimie du Solide, F-59000 Lille, France"}]}],"member":"1968","published-online":{"date-parts":[[2022,10,20]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1002\/mabi.200700106","article-title":"Biodegradation of Aliphatic and Aromatic Polycarbonates: Biodegradation of Aliphatic and Aromatic Polycarbonates","volume":"8","author":"Artham","year":"2008","journal-title":"Macromol. Biosci."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"39822","DOI":"10.1002\/app.39822","article-title":"Renaissance of Aliphatic Polycarbonates: New Techniques and Biomedical Applications: Review","volume":"131","author":"Xu","year":"2014","journal-title":"J. Appl. Polym. 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