POS1-0262
Harnessing Nickel's Dual Reactivity for the One-Pot Synthesis of Polar Polyolefin Block Copolymers
Topic
S1. Polymer Synthesis
When and Where
Sep 29, 2026
08:30 - 09:30
Room 301 (Grand Ballroom)
Session Chairs
Hae Jung SON
Boseok KANG
Presenter(s)
Muhammad Arslan (University of Houston)
Co-Author(s)
Abstract
Block copolymers (BCPs) combining nonpolar polyolefins with polar segments remain difficult to access in a one-pot manner using nickel catalysts, largely due to the intolerance of nickel complexes towards polar groups. We have demonstrated the first synthesis of polar polyolefin block copolymers enabled by rational nickel catalyst design that allows transitioning from one to another polymerization mechanism in an orthogonal fashion. A series of pre-alkylated carbyl iminopyridyl Ni(II) complexes were developed that exhibit a unique dual catalytic nature and could selectively perform coordination-insertion polymerization of ethylene in the dark, followed by photo-initiated radical polymerization of acrylates from the same growing polymer chain, leading to the formation of PE-b-P(Acrylate) BCPs. The polyethylene block length, branching density, and crystallinity are tuned through ligand design and activation conditions, while the polar block composition is varied using common acrylates, including methyl, ethyl, n-butyl, and benzyl acrylate. The resulting block copolymers span total molecular weights from ~50-240 kg/mol and incorporate polyethylene segments ranging from low-crystallinity PE segments to high-molecular-weight PE blocks.
This work demonstrates that nickel, an earth-abundant and industrially relevant metal, can be engineered to control dual polymerization pathways, providing a new platform for designing functional polyolefin block copolymers with tunable structure and properties. The approach opens practical routes toward advanced polyolefin materials that bridge commodity polymers and functional soft matter.
This work demonstrates that nickel, an earth-abundant and industrially relevant metal, can be engineered to control dual polymerization pathways, providing a new platform for designing functional polyolefin block copolymers with tunable structure and properties. The approach opens practical routes toward advanced polyolefin materials that bridge commodity polymers and functional soft matter.
