Circular olefin copolymers made de novo from ethylene and α-olefins

03 November 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Polyethylene (PE)-based materials, including ethylene homopolymers and its random or block copolymers with α-olefins, are the most produced synthetic materials globally, but current practices in their production, use, and after-use that follow the linear materials economy framework have taken a huge toll on both the environment and society. 1,2 Although several notable advances have been made in PE chemical re/upcycling, 3-10 energy-efficient and selective catalytic processes are still lacking due to the inherent chemical inertness of C-C and C-H bonds in PE. 11 Ideally, PE materials should be made de novo to have a circular, closed-loop lifecycle. 12-15 Recently, several circular polymers with closed-loop lifecycles were developed, 16-22 including recyclable high-density PE (HDPE)-like polymers. 23-25 However, production of circular ethylene/α-olefin copolymers, including high-volume, linear low-density PE (LLDPE) as well as high-value olefin elastomers and block copolymers at scale, presents a particular challenge due to difficulties in introducing branches while simultaneously installing chemical recyclability and also directly using industrial ethylene and α-olefin feedstocks. Here we show that coupling of industrial coordination copolymerization of ethylene and α-olefins with a designer functionalized chain-transfer reagent, followed by modular assembly of the resulting AB telechelic polyolefin building blocks by polycondensation, affords a series of ester-linked LLDPE and PE-based copolymers. These new materials not only retain thermomechanical properties of PE-based materials but also exhibit full chemical circularity via simple transesterification and markedly enhanced adhesion to polar surfaces.


circular polymer
olefin polymerization
olefin block copolymer
recyclable polyolefin
de novo desin

Supplementary materials

Supplementary Information
Synthesis and characterization of organozinc reagent; polymer characterizations; polymer property studies


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