Sulfur Vulcanization and Material Properties of Polyhydroxyalkanoates with Unsaturated Side Chain

This study aimed to evaluate the physical properties and biodegradability of sulfur-vulcanized polyhydroxyalkanoates (PHAs) with unsaturated side chains. As a vulcanizable PHA, poly(3-hydroxybutyrate-co-3-hydroxy-5-hexenoate) [P(3HB-co-3H5HE)] was biosynthesized with a 3H5HE fraction of 3–47 mol% using recombinant Escherichia coli and subsequently vulcanized with varying sulfur contents (2–20 per hundred resin, phr) in the presence of zinc oxide, stearic acid, and 2-mercaptobenzothiazole as curing agents. The vulcanized PHA copolymers were insoluble in chloroform, indicating the formation of a cross-linked network. Raman spectroscopy revealed the functional loss of the double bonds in the polymers. After the vulcanization with 5 phr sulfur, the tensile strength and elongation at break of P(3HB-co-47 mol% 3H5HE) increased from 0.6 MPa to 6.3 MPa and from 430% to 813%, respectively. This sample exhibited low tensile set (8%) after 200% elongation, indicating rubber-like properties. Although biodegradability decreased with increasing crosslink density, vulcanized P(3HB-co-3H5HE) exhibited a greater degradation potential than vulcanized rubber but was lower than that of non-vulcanized P(3HB-co-3H5HE). These findings demonstrate that sulfur vulcanization can enhance the resilience of unsaturated PHAs, making them suitable for elastomeric and environmental applications.