Epitaxial crystallization of precisely bromine-substituted polyethylene induced by carbon nanotubes and graphene†
Precisely substituted polyethylenes have well-defined primary structures and aggregation architecture. Herein, precisely bromine-substituted polyethylene (PE21Br) was chosen as an ideal model to investigate the substituent impact on epitaxial crystallization upon one-dimensional carbon nanotubes (CNT) and two-dimensional reduced graphene oxide (RGO) via solution crystallization. The abilities of different dimensional nanofillers to induce ordered chain packing structures were compared. Transmission electron microscopy (TEM) images showed that kebab-like and rod-like nanofiller-induced crystals were separately observed on the surfaces of CNT and graphene, and selected area electron diffraction (SAED) pattern revealed that the c-axis of the polymer chain was parallel to the surface of RGO. Fast-scan differential scanning calorimetry (Flash DSC) revealed that the melting points of the crystals grown on CNT and graphene were increased by 19 and 99 °C, respectively. More importantly, X-ray diffraction (XRD) suggested that CNT and RGO induced the transition of the crystal structure of PE21Br from the triclinic to orthorhombic form, but with different orderness. More ordered lattice structures and higher melting temperatures of PE21Br/RGO nanocomposites are ascribed to the perfect lattice matching between PE21Br and RGO. This study not only provides a method for fabricating bromine-functionalized polyolefin nanocomposites, but is also anticipated to open up a new opportunity for improving the service temperature of substituted polyethylene by means of epitaxial crystallization.