Intriguing crystallization behavior and rheological properties of radical-based crosslinked biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

A series of branched/crosslinked poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] with changing gel fractions were obtained by adding small amounts of crosslinking agents dicumyl peroxide (DCP) and triallyl isocyanurate (TAIC). The thermal and rheological properties of the samples were investigated. The chain branches formed by adding a certain amount of DCP bring in not only excess free volume which enhanced the cold crystallization ability but also defective crystals which decreased the melting temperature. Additionally, the rheological properties of branched samples were improved compared with those of neat P(3HB-co-4HB). The most intriguing result was the crystallization behavior of crosslinked P(3HB-co-4HB). The crosslinks, acting as favorable nucleation sites, can enhance the crystallization nucleation rate markedly. However, too many crosslinks could impede the transportation of macromolecular chain segments during the crystallization, resulting in a decreased crystallization rate, and the final crystallinity of crosslinked P(3HB-co-4HB) was independent of the degree of crosslinking. Furthermore, due to the formation of a gel network, crosslinked biodegradable P(3HB-co-4HB) exhibited remarkable improvement in rheological properties than branched samples, extending its processing methods, like foaming and film blowing. Accordingly, the practical applications of this biosourced and biocompatible polymer can be widely achieved.