title: Monohydroxylated poly(3-hydroxyoctanoate) oligomers and its functionalized derivatives used as macroinitiators in the synthesis of degradable diblock copolyesters.
abstract: The presence of a hydroxyl group at the end of poly(3-hydroxyoctanoate) oligomers, noted PHO oligomers, is required to prepare diblock copolymers with improved properties by ring-opening polymerization of cyclic monomer as epsilon-caprolactone. Several chemical methods such as basic hydrolysis, acid-catalyzed reaction with APTS, and methanolysis were used to prepare well-defined low molar masses PHO oligomers. The methanolysis reaction was allowed to proceed for 10-60 min to produce PHO oligomers with Mn values ranging from 20,000 to 800 g mol-1 with low polydispersity index. Detailed analysis of the MALDI-TOF mass spectra of the obtained oligomers has revealed the presence of linear structures bearing methyl ester on one side and hydroxyl end group on the other side. The same procedure was applied to poly(3-hydroxyoctanoate-co-3-hydroxyundecenoate), PHOU, a poly(3-hydroxyalkanoate) containing unsaturated units in its side chains. These oligomers were further used to initiate the polymerization of epsilon-caprolactone by varying the PHO (or PHOU) and PCL lengths. By copolymerization with epsilon-caprolactone, the properties of PHO or PHOU have been improved. The crystallinity of the obtained copolymers was modified by controlling the length of the two different blocks. The unsaturations in the side chains of the PHOU block were oxidized in acid carboxylic functions to obtain a novel artificial biopolyester. Moreover, degradation was followed to study the influence of carboxylic groups on the hydrolysis of the copolymers.
authors.affiliation: Laboratoire de Recherche sur les Polymères, UMR 7581, Université Paris 12-Val de Marne, CNRS, 2 à 8 rue H. Dunant, 94 320 Thiais, France.
authors.forename: Laurianne
authors.initials: L
authors.lastname: Timbart
authors.forename: Estelle
authors.initials: E
authors.lastname: Renard
authors.forename: Martine
authors.initials: M
authors.lastname: Tessier
authors.forename: Valérie
authors.initials: V
authors.lastname: Langlois
mesh_terms: D046911:Macromolecular Substances / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011091:Polyesters / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D046911:Macromolecular Substances; D011091:Polyesters; C088151:poly(3-hydroxyoctanoic acid)