Effect of hydrophobically modified graphene oxide on the properties of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

Nanocomposites of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3,4HB)] and hydrophobically modified graphene oxide (GO) were prepared via melt blending and characterized with respect to processability, polymer degradation, as well as thermal, rheological and mechanical properties. GO prepared via the modified Hummer's method was alkylated by reactions with butyl-, octyl- and hexadecylamine, respectively. The successful functionalisation was verified by IR spectroscopy, X-ray diffraction measurements, transmission electron microscopy and elemental analysis. The thermal decomposition temperature of the alkylated GOs increased with increasing alkyl chain length. Moreover, the alkylated GOs showed a much improved compatibility with P(3,4HB) in the melt compared to the unmodified GO, and microscopy showed an even distribution in the polymer matrix. The molecular weight of P(3,4HB) was found to decrease during the melt extrusion, and the chain degradation was found to increase after the addition of alkylated GO. However, this effect decreased with increasing alkyl chain length. Melt rheology measurements showed that percolating networks appeared at filler contents above similar to 2 wt%. These networks were detected as increases in shear storage modulus and decreased phase shifts towards more elastic materials over time and at low frequencies. During cooling of the melts, calorimetric measurements showed an increase in the crystallization temperature and enthalpy with increasing filler contents up to similar to 2 wt%. However, at higher filler contents a decreased propensity for crystallization was noted, which again indicated network formation. Tensile testing showed that the nanocomposites containing the GO with hexadecyl chains displayed the highest elongation at break and yield stress. However, the numbers were lower compared to the unfilled P(3,4HB), most probably because of the lower molecular weight of the P(3,4HB) in the nanocomposites. The results of the present study demonstrated that alkylation of GO greatly improves the compatibility with the polymer, and that the processability and thermo-mechanical properties of the nanocomposites are systematically influenced by the GO content and the alkyl chain length. (C) 2016 Elsevier Ltd. All rights reserved.