Abstract
Isosorbide telechelic bio-‐based oligomers a,b c b b a c a a J.-‐D. Rodier, V. D’Anna, N. Ritter, S. Dalicieux, C. Chamignon, P. Sautet, J.-‐P. Pascault, A. Rousseau and E. a Fleury . a Universite-‐Lyon, INSA-‐Lyon, Ingenierie des Materiaux Polymeres, IMP, UMR 5223, 69621 Villeurbanne, France b Gattefosse SAS, 69804 Saint-‐Priest, France c Universite de Lyon, CNRS, Ecole Normale Superieure de Lyon, Laboratoire de Chimie, UMR 5182, 69342 Lyon, France. Abstract The paper describes i) the structural characterization of copolymers obtained by acid catalyzed polymerization of renewable monomers: 1,3-‐propanediol (PDO) and isosorbide ii) the mechanism of etherification between isosorbide and PDO and transetherification between isosorbide and the homopolymer of PDO, polytrimethylene ether glycol (PTEG). Both experimental and computational approaches were considered. The structures of the synthesized co-‐oligomers are determined through 2D-‐NMR techniques: H-‐ C Heteronuclear Single Quantum Coherence (HSQC), H-‐ C and Heteronuclear Multiple Bond Correlation (HMBC), and COSY H-‐ H. The molar mass, the degree of polymerization and the chain-‐ends of the oligomers (PDO or isosorbide unit) were obtained through H-‐NMR. MALDI-‐TOF mass spectrometry is a complementary tool to corroborate the structures. Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis gave the first basic thermal properties of the synthesized oligomers, glass transition temperature Tg and thermal stability. DSC measurements show an increase of the copolymers’ Tg compared to PDO homopolymers. The analytical data as a whole revealed that, in our experimental conditions, the synthesized copolymers are low molar mass polymers terminated by isosorbide units, despite the presence of two hydroxyl groups on each isosorbide monomer. These structures and the limited molar mass measured suggest the coexistence of etherification and transetherification reactions evolving respectively the 5 (endo) and 2 (exo) hydroxyl functions of the isosorbide. Some copolymers containing 23 to 38 mole % of isosorbide in the polymer coupled with a molar mass ( M n ) lower than 610 g.mol-‐1 show good water solubility at 1wt-‐%. Density Functional Theory (DFT) calculations were performed in order to obtain more insight on the reactivity and the mechanisms. The presence of the solvent was considered, and the thermodynamic of the system was evaluated at the experimental temperature of reaction (150 °C).
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