Catalytic carbon–carbon bond cleavage and carbon-element bond formation give new life for polyolefins as biodegradable surfactants

File
IS_J_10459.pdf (1.55 MB)

File Embargoed Until: (2022-04-09)
Date
2021-04-09
Authors
Kanbur, Uddhav
Zang, Guiyan
Paterson, Alexander
Chatterjee, Puranjan
Hackler, Ryan
Delferro, Massimiliano
Slowing, Igor
Perras, Frédéric
Sun, Pingping
Sadow, Aaron
Journal Title
Journal ISSN
Volume Title
Publisher
Altmetrics
Authors
Research Projects
Organizational Units
Ames Laboratory
Organizational Unit
Chemistry
Organizational Unit
Journal Issue
Series
Abstract

Catalytic methods that introduce functional groups via carbon–carbon bond cleavage steps have typically been limited to moieties activated by strain or by directing groups, with few transformations engaging the bonds of only sp3-hybridized carbon atoms in saturated hydrocarbons. Here, we report the conversion of catenated carbon chains in polyolefins, which currently represent >50% of discarded plastics, into shorter aliphatic alkylaluminum species via a sequence of zirconation via C–H bond activation, β-alkyl elimination for carbon–carbon bond cleavage, and heterobimetallic alkyl group exchange for carbon–aluminum bond formation. The versatility of aliphatic alkylaluminum species is exemplified by their subsequent conversion into high-value fatty acids or alcohols, which have applications as biodegradable surfactants and detergents. A technoeconomic analysis indicates that fatty alcohols produced from discarded polyolefins are cost competitive with conventional syntheses. Thus, this process could ameliorate economic and environmental challenges of the plastic-waste crisis.

Description
Keywords
carbon–carbon bond alumination, polyolefin degradation, fatty alcohols, fatty acids, polymer upcycling, β-alkyl elimination, biodegradable products, surfactants
Citation
DOI
Collections