Differences between Ziegler–Natta and Single‐Site Linear Low‐Density Polyethylenes as Characterized by Inverse Gas Chromatography

Summary: Zero‐pressure weight‐fraction‐based Henry's constants $(H_{{\rm 12}}^0 )$ of two alkanes, two alkenes, and benzene in Ziegler–Natta (ZN) and single‐site (ss) linear low‐density polyethylenes (LLDPE) with different average branch contents, molecular‐weight averages ( $\overline M _{\rm n}$ and $\overline M _{\rm w}$ ), and polydispersity indices (PDI) were measured in the temperature range of 170 to 230 °C using the technique of inverse gas chromatography. For both types of LLDPEs, the measured $H_{{\rm 12}}^0$ was insensitive to molecular weight and PDI. However, the branch content dependence differed significantly. In particular, ZN‐LLDPE exhibited a strong branch content dependence on $H_{{\rm 12}}^0$ while ss‐LLDPE did not. In fact, depending on the temperature and solvent used, $H_{{\rm 12}}^0$ of ZN‐LLDPE could drop as much as 21% with an increase in an average branch content from 13 to 35 branches per 1 000 backbone carbons, while the differences of $H_{{\rm 12}}^0$ between ss‐LLDPEs with comparable differences in branch content were well within experimental uncertainties (5%). This observation is also supported by the fact that comparable ZN‐ and ss‐LLDPEs exhibited larger differences in $H_{{\rm 12}}^0$ at higher average branch contents. The above findings strongly suggested that the liquid morphologies of ZN‐ and ss‐LLDPEs differ considerably. In particular, the local chain conformation and free volume characteristics (i.e., the size distribution and/or spatial distribution of the free volume holes) of them are rather different. Such differences become more pronounced at higher temperatures.The weight‐fraction‐based Henry's constant of n ‐hexane and hex‐1‐ene in Ziegler–Natta (ZN) and single‐site (ss) linear low‐density polyethylenes (LLDPE) with different average branch contents.