3/27/24, 10:13 AM A commercially viable solution process to control long-chain branching in polyethylene | Science

A commercially viable solution process to control

long-chain branching in polyethylene
ROBERT D. FROESE , DANIEL J. ARRIOLA, JAAP DEN DOELDER, JIANBO HOU , TERESITA KASHYAP , KERAN LU, LUCA MARTINETTI , AND BRYAN D. STUBBERT

Authors Info & Affiliations

ENCE14 Mar 2024Vol 383, Issue 6688pp. 1223-1228DOI: 10.1126/science.adn3067

1,988 CHECK ACCESS

Editor’s summary
Low-density polyethylene (LDPE) is widely applied in plastic films and other pliable
products. It derives its properties from a branched rather than straight molecular structure,
which requires an energy-intensive, high-pressure synthesis technique. Froese et al. report a
distinct method to achieve long-chain branching under milder, solution-phase conditions.
Their catalyst can assemble two chains at once, linked through the use of a small amount of
diene mixed in with the ethylene, to create a ladder-like geometry. The resulting plastic has
properties comparable to LDPE. —Jake S. Yeston

Abstract
In polyolefins, long-chain branching is introduced through an energy-intensive, high-
pressure radical process to form low-density polyethylene (LDPE). In the current work, we
demonstrated a ladder-like polyethylene architecture through solution polymerization of
ethylene and less than 1 mole % of α,ω-dienes, using a dual-chain catalyst. The ladder-
branching mechanism requires catalysts with two growing polymer chains on the same
metal center, thus enchaining the diene without the requirement of a steady-state
concentration of pendant vinyl groups. Molecular weight distributions lacking a high–
molecular weight tail, distinctive Mark-Houwink signatures, nuclear magnetic resonance
characterization, and shear and extensional rheology consistent with highly branched
polyethylene architectures are described. This approach represents an industrially viable
solution-polymerization process capable of producing controlled long-chain branched
polyethylene with rheological properties comparable to those of LDPE or its blends with
linear low-density polyethylene (LLDPE).

https://www.science.org/doi/10.1126/science.adn3067 1/1