Perfectly Controlled Lamella Thickness and Thickness Distribution: A Morphological Study on ADMET Polyolefins



Summary: Lamella thickness distribution (LTD) plays a critical role in determining the mechanical properties of polyethylene. LTD is predominantly governed by the intermolecular chemical composition distribution, but intrachain heterogeneity also results in a broadened LTD. Polyethylene synthesized by acyclic diene metathesis (ADMET) contains pristine microstructures free from inter and intrachain heterogeneity and therefore represent ideal models to investigate these phenomena. The crystalline structures of ADMET polyethylene with ethyl or n-hexyl branches every 21st backbone carbon (EB21and EO21, respectively) were characterized by transmission electron microscopy (TEM), small X-ray scattering and wide angle X-ray diffraction (SAXS and WAXD), and differential scanning calorimetry (DSC). The samples were crystallized for various periods at temperatures near the DSC crystallization peak temperatures: 10 °C for EB21 and 0 °C for EO21. TEM observation exhibited that EB21 displays straight lamellar crystals with axialitic organization and an average thickness of about 55 Å. This corresponds to twice the ethylene sequence length between branches, suggesting that one lamellar stem spans three branches and includes one ethyl branch within the lamella. The lamella thickness distribution was very narrow compared with that of the cross-fraction of ethylene/1-butene copolymer prepared via Ziegler-Natta polymerization. Similarly it was found from the same characterization methods that EO21 also displays a narrow lamella thickness distribution albeit with thinner lamellae, averaging 25–26Å thick. Judging from this lamella thickness, EO21 is considered to have a lamella stem composed of a single ethylene sequence between two braches, suggesting that the n-hexyl branch is entirely excluded from a crystalline phase.