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Mechanism of the Living Lactide Polymerization Mediated by Robust Zinc Guanidine Complexes
Author(s) -
Börner Janna,
dos Santos Vieira Ines,
Pawlis Alexander,
Döring Artjom,
Kuckling Dirk,
HerresPawlis Sonja
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002690
Subject(s) - lactide , guanidine , mechanism (biology) , polymerization , zinc , chemistry , living polymerization , polymer chemistry , organic chemistry , polymer , philosophy , radical polymerization , epistemology
Zinc bis(chelate) guanidine complexes promote living lactide polymerization at elevated temperatures. By means of kinetic and spectroscopic analyses the mechanism has been elucidated for these special initiators that make use of neutral N‐donor ligands. The neutral guanidine function initiates the polymerization by a nucleophilic ring‐opening attack on the lactide molecule. DFT calculations on the first ring‐opening step show that the guanidine is able to act as a nucleophile. Three transition states were located for ligand rearrangement, nucleophilic attack, and ring‐opening. The second ring‐opening step was modeled as a representation for the chain growth because here, the lactate alcoholate opens the second lactide molecule via two transition states (nucleophilic attack and ring‐opening). Additionally, the resulting reaction profile proceeds overall exothermically, which is the driving force for the reaction. The experimental and calculated data are in good agreement and the presented mechanism explains why the polymerization proceeds without co‐initiators.

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