Creation of fully degradable and mechanically robust poly(4-hydroxybutyrate) films by filling modified starch

Chemically synthesized poly(4-hydroxybutyrate) (P4HB) is a new generation of biomass-derived and degradable semi-crystalline polymer with good comprehensive properties, but high costs limit its application. Starch, as an inexpensive natural polymer, can reduce the cost of P4HB products. However, starch lacks thermoplastic behavior and has poor compatibility with P4HB, thus its extensive use will inevitably impair the mechanical properties of P4HB. In this study, the ball-milling starch grafting process is adopted, which can simultaneously solve the two major deficiencies of starch, and the prepared ball-milling starch-g-polycaprolactone (BSt-g-PCL) has thermoplasticity and better compatibility with P4HB. BSt-g-PCL can melt near 55 °C, and the interweaving of its molecular chains with P4HB reduces the binding energy (E_interaction) of both, making the phase interface blurred or even disappear. Therefore, the elongation at break retention (R_EB) of P4HB/BSt-g-PCL can increase from 37.1 % to 74.3 % compared to P4HB/starch at the same filling (70 Phr). Additionally, BSt-g-PCL can exert the effect of accelerating P4HB degradation and still make it maintain excellent anti-aging ability. The ball-milling starch graft process provides a simple and effective method for the preparation of inexpensive fully biodegradable P4HB composite films with excellent mechanical properties.