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

Uddhav Kanbur, Iowa State University and Ames Laboratory
Guiyan Zang, Argonne National Laboratory
Alexander L. Paterson, Ames Laboratory
Puranjan Chatterjee, Iowa State University and Ames Laboratory
Ryan A. Hackler, Argonne National Laboratory
Massimiliano Delferro, Argonne National Laboratory
Igor I. Slowing, Iowa State University and Ames Laboratory
Frédéric A. Perras, Ames Laboratory
Pingping Sun, Argonne National Laboratory
Aaron D. Sadow, Iowa State University and Ames Laboratory

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.