Branch length distribution in TREF fractionated polyethylene

Commercial polyethylene is typically heterogeneous in molecular weight as well as in molecular topology due to variability in catalyst systems and catalyst activity. Further, processing of polyethylene after polymerization may also result in changes to the structure. While quantification of molecular weight is routine using gel permeation chromatography (GPC); quantification of the heterogeneity in molecular topology and microstructure is more difficult. In this paper, a novel method is used to examine the structure and branch content of a linear low-density polyethylene (LLDPE). The method uses a scaling model to analyze small-angle neutron scattering (SANS) data from dilute solutions of a series of LLDPE fractions. The scaling approach quantifies short-chain and long-chain branch content in polymers concurrently, thereby illustrating the distribution of these branches in the polyethylene fractions. Additionally, new quantities such as the average long-chain branch length and hyperbranch content are measured to provide further insight into the structure of these polymers. LLDPE used in this study is fractionated using temperature rising elution fractionation (TREF). Results from the analysis of these fractions show evidence of long-chain branching in commercial LLDPE which could be partly attributed to post-synthesis processing conditions.