[en] The use of different phosphazene bases has been investigated as catalysts in polymerization of [R,S]-4-benzyloxycarbonyl-3,3-dimethyl-2-oxetanone (dMMLABz) in presence of carboxylic acids used as initiators. Whatever the catalyst considered (P1-t-Bu, P2-t-Bu, or P4-t-Bu) a very good control over the polymerization has been obtained in terms of polyester molecular weights and end-groups fidelity as attested by spectroscopic techniques such as 1H NMR, gel permeation chromatography (GPC) and matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) experiments. Characterized by a complete absence of transfer reactions, the system allows for the generation of very high molecular weight PdMMLABz trough a mechanism selectively involving the 'O-alkyl' scission of the ß-lactone monomer. A clear dependence of the basicity of the phosphazene catalyst on the overall polymerization kinetics has been observed where the most basic catalytic species, i.e., 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranyl-idenamino]-2?5,4?5-catenadi(phosphazene) (P4-t-Bu), shows the highest active ion-pair. Accordingly, P4-t-Bu allowed for the synthesis of PdMMLABz chains characterized by a number-average molecular weight higher than 1.5 × 106 g mol-1.
Disciplines :
Chemistry
Author, co-author :
De Winter, Julien ; Université de Mons > Faculté des Sciences > Synthèse et spectrométrie de masse organiques
Coulembier, Olivier ; Université de Mons > Faculté des Sciences > Matériaux Polymères et Composites
Gerbaux, Pascal ; Université de Mons > Faculté des Sciences > Synthèse et spectrométrie de masse organiques
Dubois, Philippe ; Université de Mons > Faculté des Sciences > Matériaux Polymères et Composites
Language :
English
Title :
High molecular weight poly(a,a',b-trisubstituted b-lactones) as generated by metal-free phosphazene catalysts
Publication date :
01 December 2010
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society (ACS), United States - District of Columbia
Volume :
43
Issue :
24
Pages :
10291-10296
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S816 - Matériaux Polymères et Composites S836 - Synthèse et spectrométrie de masse organiques
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
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