Effect of the Sequence Length Distribution on the Lamellar Crystal Thickness and Thickness Distribution of Polyethylene: Perfectly Equisequential ADMET Polyethylene vs Ethylene/α-Olefin Copolymer

The morphology of ADMET-synthesized polyethylene with n-butyl branches precisely spaced on every 39th carbon (EH39) was studied in comparison with an ethylene/1-hexene addition copolymer possessing the same branching probability, the goal being to elucidate the effect of the intramolecular sequence length heterogeneity on the lamella crystal thickness and its distribution: EH39 was found to have an orthorhombic crystalline polymorphism, which is normal for commercialized polyethylenes and different from that of the other ADMET polyethylenes with shorter CH(2) spacing (C15, C21). EH39 exhibits a narrow lamella thickness distribution; the average thickness (l(c,av)) corresponds exactly to the space length between two consecutive branches, suggesting the complete exclusion of n-butyl branches from the crystal stem. The average thickness, l(c,av). mentioned above is also coincident with that obtained from WAXS and SAXS. On the other hand, the 1-hexene copolymer forms much thicker lamellae and a-broader thickness distribution than ADMET polyethylene. Here, the average thickness l(c,av). determined by TEM observation of the copolymer is 1.5 times larger than that calculated from the most probable ethylene sequence length obtained from (13)C NMR, or for a theoretical ethylene sequence length distribution, indicating that the lamellae are composed predominantly of the sparsely branched longer ethylene sequences' that are statistically included. The intramolecular sequence distribution is considered significant to determine the lamella thickness and thickness distribution for short chain-branched polyethylenes with a narrow intermolecular chemical composition distribution.