Structural and Morphological Inhomogeneity of Short-Chain Branched Polyethylenes in Multiple-Step Crystallization

Abstract

Three commercial metallocene-catalyst synthesized short-chain branched polyethylene (SCBPE) samples with similar molecular weights and molecular weight distributions were investigated in terms of their molecular structural (comonomer sequences and compositions) inhomogeneity and crystal morphology. Two of these samples [SCBPE(B1) and SCBPE(B2)] contained different ratios of a butene comonomer (20.7 and 26.8 SCB/1000 carbons, respectively), while the third sample, SCBPE(H), contained a branched hexane comonomer (7.8 SCB/1000 carbons). A linear PE fraction was also investigated for comparison. Differential scanning calorimetry (DSC) results indicate that multiple-step isothermal (thermal segregation) experiments lead to multiple endothermic melting processes in these SCBPEs during heating, a phenomenon that was not observed in the linear PE. Wide-angle X-ray diffraction (WAXD) experiments show that all of these SCBPEs possess an orthorhombic crystal lattice with different crystallinities. Linear coefficients of thermal expansion along both the a- and b-axes of the PE crystals were also determined using WAXD at different temperatures. This lateral lattice expansion is critically associated with the comonomer size and composition ratio of the SCB series. Small-angle X-ray (SAXS) scattering results of the thermal segregated samples obtained during heating required a differential scattering data treatment. It was found that the long period for each isothermal crystallization step was different and increased with increasing temperature. By increasing the comonomer composition at a constant temperature, the long period was also increased, although the thickness of the crystal lamellae decreased. This was due to an increase of the noncrystalline layer thickness between two neighboring lamellae. The crystalline morphology was observed under transmission electron microscopy (TEM). During multiple-step isothermal crystallization, the crystalline morphology exhibited a clearly separated lamellar domain texture. All of the experimental results presented suggest that a phase separation occurs during multiple-step crystallization due to the inhomogeneity that exists in these SCBPE molecular structures. These samples may thus possess an intermolecular heterogeneity in comonomer composition and sequence.

ACKNOWLEDGMENT

This work was supported by DMR-9617030 from the National Science Foundation, BP Chemical Company, the Phillips Petroleum Company, and the NSF/State/Industrial Center for Molecular and Microstructure of Composites.