Multi-scale instrumental analyses of plasticized polyhydroxyalkanoates (PHA) blended with polycaprolactone (PCL) and the effects of crosslinkers and graft copolymers

Abstract

Details of the mechanism underlying the tensile properties of plasticized polyhydroxyalkanoates (PHA) including poly(butylene succinate) (PBS) were investigated by blending with poly(ε-caprolactone) (PCL) as well as the addition of compatibilizers. Multi-scale instrumental analyses employed micro-focus X-ray CT to provide micro-scale morphology information on the order of ten microns while solid-state NMR spectral and relaxation time analyses contributed knowledge of the environment and molecular mobility of each constituent at the molecular to nano-scale. The blend of plasticized PHA with 50% PCL adopted a sea-island morphology to improve elongation at break in a quasi-static tensile test, which was dominated by the tensile properties of the added PCL. However, impact tensile properties were less improved by PCL addition, because its molecular mobility was suppressed by blending. Meanwhile, peroxy crosslinkers changed the sea-island morphology to homogenous in X-ray CT observations. Although the homogenous morphology sharply lowered the elongation at break in a quasi-static tensile test, the homogenous morphology improved impact tensile properties. Furthermore, graft polymers having acrylonitrile–styrene side-chains did not change the sea-island morphology but increased the molecular mobility of PBS in the plasticized PHA. This weak interaction between the plasticized PHA and PCL improved tensile properties in both quasi-static and impact tensile tests.