Determination of Chain Transfer Constants of Alcohols for High‐Pressure Polyethylene Polymerization

Abstract In low‐density polyethylene (LDPE) production, low‐molecular‐weight species are used as chain transfer agents (CTAs). They reduce the degree of polymerization, which has an impact on the polymer properties, such as processability. To specifically adjust the product properties, a detailed understanding of the transfer kinetics to CTAs is indispensable. Thus, the transfer activity of various primary, secondary, and tertiary alcohols as well as diols was investigated experimentally between 120 °C and 250 °C at 2000 bar. The results were evaluated using the Mayo and chain length distribution (CLD) method, and the latter was found to give more reliable results. It was observed that the hydroxy group systematically increases transfer activity compared to alkanes. Additionally, a linear increase of transfer activity with the number of hydrogen atoms is found.