[en] A well-defined high molecular weight poly(3-hydroxybutyrate) was synthesized by 'living'/controlled ring-opening polymerization (ROP) of ß-butyrolactone (BL) using a metal-free catalytic system. The ROP was initiated from either primary alcohol or carboxylic acid added with 1 equiv of a stable carbene, i.e., 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene carbene, 1. Interestingly, perfect control over molecular weight (Mn up to 32000 g·mol-1), molecular weight distribution (Mw/Mn 1.1 - 1.3) and end group fidelity was attained using t-BuOH as the only polymerization solvent at 80 °C. Structural and kinetics studies highlighted an anionic polymerization mechanism where the protonated 1 (1-H) played the role of associated counterion. Attesting for the control of the ROP, amphiphilic block copolymers were further synthesized by polymerization of BL from poly(ethylene oxide) a-methoxy, ?-carboxylic acid macroinitiator while their tensioactive properties were evidenced by the pendant drop method.
Disciplines :
Chemistry
Author, co-author :
Coulembier, Olivier ; Université de Mons > Faculté des Sciences > Matériaux Polymères et Composites
Delva, X.
Hedrick, James L.
Waymouth, B.M.
Dubois, Philippe ; Université de Mons > Faculté des Sciences > Matériaux Polymères et Composites
Language :
English
Title :
Synthesis of biomimetic poly(hydroxybutyrate): alkoxy- and carboxytriazolines as latent ionic initiator
Publication date :
27 November 2007
Journal title :
Macromolecules
ISSN :
0024-9297
Publisher :
American Chemical Society (ACS), United States - District of Columbia
Volume :
40
Issue :
24
Pages :
8560-8567
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S816 - Matériaux Polymères et Composites
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Duda, A. J. Polym. Sci., Part A: Polym. Chem. 1992, 30, 21.
(a) Kurcok, P.; Sigma, J.; Jedlinski, Z. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 2184.
(b) Rieth, L. R.; Moore, D. R.; Lobkovski, E. B. Coates, G. J. Am. Chem. Soc. 2002, 124, 15239.
(a) Coulembier, O.; Mespouille, L.; Hedrick, J. L.; Waymouth, R. M.; Dubois, Ph. Macromolecules 2006, 39, 4001.
(b) Coulembier, O.; Lohmeijer, B. G. G.; Dove, A. P.; Pratt, R. C.; Mespouille, L.; Culkin, D. A.; Benight, S. J.; Dubois, P.; Waymouth, R. M.; Hedrick, J. L. Macromolecules 2006, 39, 5617.
Carboxylic acid end groups have been identified by reaction of ω-carboxylic acid PBL with excess of trimethylsylildiazomethane. 1H-NMR spectrum attests for the appearance of the expected ω-methyloxycarbonyl protons at δ = 3.55 ppm (Figure S2).
Cowman, J. A.; Clyburne, J. A. C.; Davidson, M. G.; Harris, R. L. W.; Howard, J. A. K.; Küpper, P.; Leech, M. A.; Richards, S. P. Angew. Chem., Int. Ed. 2002, 41, 1432.
Zalipsky, S.; Gilon, C.; Zilkha, A. Eur. Polym. J. 1983, 1177.
Mukerjee, P.; Mysels, K. J. Critical Micelle Concentration of Aqueous Surfactant Systems; NSRDS-NBS 36; U.S. Government Printing Office: Washigton, DC, 1971.
Garibi, H.; Palepu, R.; Tiddy, G. J. T.; Hall, D. G.; Wyne-Jones J. Chem. Soc., Commun. 1990, 2, 115.
