Miscibility and Phase Structure of Blends of Poly(ethylene oxide) with Poly(3-hydroxybutyrate), Poly(3-hydroxypropionate), and Their Copolymers

Abstract

The miscibility and phase behavior of poly(ethylene oxide) (PEO) blends with poly(3hydroxybutyrate) (P(3HB)), poly(3-hydroxypropionate) (P(3HP)), and poly(3-hydroxybutyrate-co-3-hydroxypropionate)s (P(3HB-co-3HP)s) have been investigated by differential scanning calorimetry (DSC) and high-resolution solid-state 13 C nuclear magnetic resonance (NMR). Four bacterial P(3HB-co-3HP) samples with 3HP contents of 15, 25, 46, and 76 mol % have been used in order to investigate possible influence of the sequence structure of P(3HB-co-3HP)s on the miscibility and phase behavior of blends. These four P(3HB-co-3HP) samples have different thermal properties and crystallizability depending on the 3HP contents. The DSC thermal behavior of the blends revealed that the blends of PEO with P(3HB), P(3HP), and P(3HB-co-3HP)s were miscible over the whole composition range but the crystallization of blend components followed by phase separation exerted much influence on the phase structure of the blends. The results from solid-state NMR spectroscopy showed that the 50/50 binary blends of P(3HB)/ PEO, P(3HB-co-15%3HP)/PEO, P(3HB-co-25%3HP)/PEO, and P(3HP)/PEO were phase-separated due to the presence of crystalline phase but miscible to some extent. Two components in these blend were found to be mixed on a range greater than 30-40 nm, with two crystalline phases and an amorphous phase of miscible two components coexisting.

Thermal degradation of poly(3-hydroxybutyrate)/poly(ethylene oxide) blends: Thermogravimetric and kinetic analysis

“…Blending of PHB with another kind of polymer may improve its properties and processability. PHB has been reported to be miscible with a few chemically synthesized polymers, such as poly(ethylene oxide)(PEO) [4][5][6][7][8][9][10]. PEO is semi-crystalline, biocompatible, biodegradable, non-ionic and water-soluble polymer of considerable industrial significance which finds applications in many different branches of industry [11].…”

“…PEO is semi-crystalline, biocompatible, biodegradable, non-ionic and water-soluble polymer of considerable industrial significance which finds applications in many different branches of industry [11]. Blending PHB with PEO was expected to give practical products that might be applied in biomedical materials and other fields [9]. Hence, miscibility, mechanical, optical, morphological and thermal properties of PHB/PEO blends has already been studied in the literature [4][5][6][7][8][9][10].…”

Poly(3-Hydroxypropionate): a Promising Alternative to Fossil Fuel-Based Materials

“…The melting temperature is lowest in poly(3HP-co-3HB)s with 3HP content of between 50 and 80 mol%. In the same range of content, fusion enthalpy is also lowest (19,20,38,43,56 (Fig. 2).…”

“…We now focus on the impact of various levels of 3HP content on chemical and physical characteristics with regard to industrial applications. The T g decreases linearly with increasing 3HP moieties (16,20,43,56). The melting temperature is lowest in poly(3HP-co-3HB)s with 3HP content of between 50 and 80 mol%.…”

Miscibility and Physical Properties of Poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)/Poly(ethylene oxide) Binary Blends

“…[25] The PEO (M v ¼ 3.0 Â 10 5 g Á mol À1 ) was found to be miscible with bacterial P(3HB), chemosynthesized P(3HP) and bacterial poly(3-hydroxybutyrate-co-3-hydroxypropionate) [P(3HB-co-3HP)] copolymers in the amorphous phase over the whole blend composition range. [26] The miscibility of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] with PEO (M w ¼ 1.0 Â 10 5 g Á mol À1 ) was also investigated and they were found to be miscible in molten state, at least in the marginal composition ranges, where one of the components was in excess. [27] The miscibility of P(3HB-co-3HHx)/PEG and P(3HB-co3HHx)/methoxy poly(ethylene glycol) (MPEG) has been reported by Lim et al [28] Both the blend systems were found to be miscible in the melt state.…”