Biobased and biodegradable polymers (BBDs) such as poly(3-hydroxy-butyrate), PHB, and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) are considered attractive alternatives to fossil-based plastic materials since they are more environmentally friendly. One major problem with these compounds is their high crystallinity and brittleness. In order to generate softer materials without using fossil-based plasticizers, the suitability of natural rubber (NR) as an impact modifier was investigated in PHBV blends. Mixtures with varying proportions of NR and PHBV were generated, and samples were prepared by mechanical mixing (roll mixer and/or internal mixer) and cured by radical C–C crosslinking. The obtained specimens were investigated with respect to their chemical and physical characteristics, applying a variety of different methods such as size exclusion chromatography, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermal analysis, XRD, and mechanical testing. Our results clearly indicate that NR–PHBV blends exhibit excellent material characteristics including high elasticity and durability. Additionally, biodegradability was tested by applying heterologously produced and purified depolymerases. pH shift assays and morphology analyses of the surface of depolymerase-treated NR–PHBV through electron scanning microscopy confirmed the enzymatic degradation of PHBV. Altogether, we prove that NR is highly suitable to substitute fossil-based plasticizers; NR–PHBV blends are biodegradable and, hence, should be considered as interesting materials for a great number of applications.

The single crystal X-ray analysis of the ester-functionalized 2-oxazoline, methyl 3-(4,5-dihydrooxazol-2-yl)propanoate, revealed Π-electron delocalization along the N–C–O segment in the 2-oxazoline pentacycle to significant extent, which is comparable to its counterpart along the O–C–O segment in the ester. Quantum chemical calculations based on the experimental X-ray geometry of the molecule supported the conjecture that the N–C–O segment has a delocalized electronic structure similar to an ester group. The calculated bond orders were 1.97 and 1.10 for the N=C and C–O bonds, and the computed partial charges for the nitrogen and oxygen atoms of \(-\)0.43 and \(-\)0.44 were almost identical. In the ester group, the bond orders were 1.94 and 1.18 for the C–O bonds, while the partial charges of the oxygen atom are \(-\)0.49 and \(-\)0.41, which demonstrates the similar electronic structure of the N–C–O and O–C–O segments. In 2-oxazolines, despite the higher electronegativity of the oxygen atom (compared to the nitrogen atom), the charges of the hetero atoms oxygen and nitrogen are equalized due to the delocalization, and it also means that a cationic attack on the nitrogen is possible, enabling regioselectivity during the initiation of the cationic ring-opening polymerization of 2-oxazoline monomers, which is a prerequisite for the synthesis of materials with well-defined structures.