Crystallinity and transitions in ethylene hexene copolymers

Copolymers of ethylene with hexene-1 have been prepared by catalytic polymerization. Three types of specimens were studied: (a) as the polymerized material; (b) the same after extraction with heptane; (c) the low molecular weight extract. These specimens were subjected to one or more of the following characterization techniques: Mn by several methods, X-ray diffraction, GPC, DSC, Rheovibron at 110 Hz, and Tg by an ESR spin probe technique. The hexene content of the extracted polymer did not exceed 4 mol%; that in the extract was as high as 89.5%. The characterization data and dynamic mechanical loss results in this paper have been examined in the context of an exhaustive study of ethylene-ethylene-α-olefin copolymers by Shirayama et al. with some additional details by Wilson et al. All Tg data are summarized in the form of a plot of temperature vs log (wt% hexene-1). It is emphasized that increasing hexene content decreases crystallinity, crystallite size and molecular weight, so that caution is required in interpreting results. For high mol wt low hexene-1 whole and extracted polymers, the spin probe method gives Tg for the amorphous phase whereas Rheovibron data reflect Tβ( >Tg) for the composite amorphous-crystallite specimens. The ESR data indicate that Tg for amorphous PE, called Tg(L), is very close to 200 K which is above and distinct from Tγ at c, 150 K. It would still be desirable to investigate a series of ethylene-hexene-1 copolymers over the entire composition range at essentially constant, high molecular weight.