The development and use of novel materials is one of the main tasks of industrial, biomedical, and environmentally safe technologies. Polyhydroxyalkanoates (PHAs) – biodegradable biocompatible polyesters of microbial origin – are among the most promising materials, which can be used in various areas. The authors’ collection of highly productive strains and original technologies were used to synthesize a family of PHA heteropolymers composed of such monomer units as 3-hydroxybutyrate (3HB), 4-hydroxybutyrate (4HB), 3-hydroxyvalerate (3HV), and 3-hydroxyhexanoate (3HHx).
Properties of the polymers were investigated using NMR, DSC, chromatography-mass spectrometry, gel permeation chromatography, and X-ray structure analysis. The degree of crystallinity of two-component PHAs was lower than that of poly-3HB, and the effect of 3HHx and 4HB components was greater than the effect of 3HV. An additive effect of incorporation of 4HB, 3HV, and 3HHx was revealed for PHA terpolymers, which had exceptionally low degrees of crystallinity: for instance, poly-3HB/4HB/3HV was actually amorphous, with the crystalline phase varying from 9 to 22%, depending on monomer fractions. Higher fractions of 4HB, 3HV, and 3HHx caused a decrease in melting temperature and thermal decomposition temperature of the copolymers as compared with poly-3HB, while the thermoplasticity of the polymers was not affected. The PHA terpolymers had lower molecular weights than PHA bipolymers.
Films prepared from all PHA terpolymers had much higher mechanical strength and elasticity than poly-3HB films.
Thus, we have developed a fundamental approach to the production of PHAs with different composition, with tailored physical and mechanical properties.