Biodegradable Polyhydroxyalkanoates with a Different Set of Valerate Monomers: Chemical Structure and Physicochemical Properties

The properties, features of thermal behavior and crystallization of copolymers containing various types of valerate monomers were studied depending on the set and ratio of monomers. We synthesized and studied the properties of three-component copolymers containing unusual monomers 4-hydroxyvalerate (4HV) and 3-hydroxy-4-methylvalerate (3H4MV), in addition to the usual 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) monomers. The results showed that P(3HB-co-3HV-co-4HV) and P(3HB-co-3HV-co-3H4MV) terpolymers tended to increase thermal stability, especially for methylated samples, including an increase in the gap between melting point (Tmelt) and thermal degradation temperature (Tdegr), an increase in the melting point and glass transition temperature, as well as a lower degree of crystallinity (40-46%) compared with P(3HB-co-3HV) (58-66%). The copolymer crystallization kinetics depended on the set and ratio of monomers. For terpolymers during exothermic crystallization, higher rates of spherulite formation (Gmax) were registered, reaching, depending on the ratio of monomers, 1.6-2.0 µm/min, which was several times higher than the Gmax index (0.52 µm/min) for the P(3HB-co-3HV) copolymer. The revealed differences in the thermal properties and crystallization kinetics of terpolymers indicate that they are promising polymers for processing into high quality products from melts.