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Radically initiated polymerization of a methacryloylamido‐terminated saccharide, 1. Monomer synthesis, homopolymerization and characterizations
Author(s) -
Badey Bérangère,
Boullanger Paul,
Domard Alain,
Cros Philippe,
Delair Thierry,
Pichot Christian
Publication year - 1996
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.1996.021971118
Subject(s) - virial coefficient , radius of gyration , polymer chemistry , monomer , polymerization , chemistry , tacticity , intrinsic viscosity , polymer , solvent , hydrodynamic radius , gyration , copolymer , organic chemistry , thermodynamics , geometry , mathematics , physics
A methacrylamido‐terminated saccharide, 6‐deoxy‐6‐methacryloylamido‐ D ‐glucopyranose (MAG), was synthesized using a new and easy pathway. Kinetics of the radically initiated solution homopolymerization of this monomer was investigated at 50°C using 4,4′‐azobis(4‐cyanopentanoic acid); the obtained k p / k t 1/2 value around 1.0 mol −1/2 ċ L 1/2 ċ s −1/2 is indicative of the strong ability of MAG to polymerize ( k p and k t being the rate constants of propagation and termination, respectively). The chemical structure of the homopolymer, as analyzed by 13 C NMR spectroscopy shows a tacticity which is in favor of a syndiotactic configuration resulting from the bulkiness of the side group. The dimensional characteristics of the polymers were studied by light scattering as an on‐line detection in size exclusion chromatography (SEC). As expected from the k p / k t 1/2 value, high weight‐average molecular weights were obtained. The small average radii of gyration were found to reflect a relatively compact structure in water due to inter‐ and intramolecular interactions; viscosity studies in various solvents as well as values of the second virial coefficient corroborate such a behavior which reflects that water is a poor solvent for poly(MAG).