Miscibility of Blends of Biodegradable Polymers and Copolymers with Different Plasticizers

Miscibility between components of different plasticizer(A)/solvent(B)/biodegradable polymer(C) ternary systems with H-bonding has been compared. Systems were formed by two H-donor phenolic plasticizers, 4-nonylphenol (NP) and 4:4'-dihydroxydiphenylmethane (BPF); an H-acceptor solvent, epichlorohydrin (ECH); and H-acceptor poly(3-hydroxybutyrate) (PHB) or poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBHV) copolymers. Blend miscibility is the result of the balance of three competitive H-bondings: plasticizer self-association (AA), plasticizer-solvent (AB) and plasticizer-polymer (AC) interassociations. The strength and extent of such specific interactions have been experimentally monitored by fluorescence spectroscopy either in solution or in solid state. Theoretical modelling has been conducted with a recent thermodynamic approach based on two free-energy excess functions.