Synthesis and physical properties of polyhydroxyalkanoate (PHA)-based block copolymers: A review

Polyhydroxyalkanoates (PHAs) are a group of natural polyesters that are synthesised by microorganisms. In general, their thermoplasticity and (in some forms) their elasticity makes them attractive alternatives to petrochemical-derived polymers. However, the high crystallinity of some PHAs - such as poly(3-hydroxybutyrate) (P3HB) - results in brittleness and a narrow processing window for applications such as packaging. The production of copolymeric PHA materials is one approach to improving the mechanical and thermal properties of PHAs. Another solution is the manufacture of PHA-based block copolymers. The incorporation of different polymer and copolymer blocks coupled to PHA, and the resulting tailorable microstructure of these block copolymers, can result in a step-change improvement in PHA-based material properties. A range of production strategies for PHA-based block copolymers has been reported in the literature, including biological production and chemical synthesis. Biological production is typically less controllable, with products of a broad molecular weight and compositional distribution, unless finely controlled using genetically modified organisms. By contrast, chemical synthesis delivers relatively controllable block structures and narrowly defined compositions. This paper reviews current knowledge in the areas of the production and properties of PHA-based block copolymers, and highlights knowledge gaps and future potential areas of research.