Iron-catalysed synthesis and chemical recycling of telechelic 1,3-enchained oligocyclobutanes

Autor: Joseph A. Throckmorton, C. Rose Kennedy, Sarah J. Mattler, Paul J. Chirik, Megan Mohadjer Beromi, Carpenter Alex E, Jarod M. Younker
Rok vydání: 2021
Předmět:
Zdroj: Nat Chem
ISSN: 1755-4349
1755-4330
DOI: 10.1038/s41557-020-00614-w
Popis: Closed-loop recycling offers the opportunity to mitigate plastic waste through reversible polymer construction and deconstruction. Although examples of chemical recycling of polymers are known, few have been applied to materials derived from abundant commodity olefinic monomers, which are the building blocks of ubiquitous plastic resins. Here we describe a [2+2] cycloaddition/oligomerization of 1,3-butadiene to yield a previously unrealized telechelic microstructure of (1,n′-divinyl)oligocyclobutane. This material is thermally stable, has stereoregular segments arising from chain-end control, and exhibits high crystallinity even at low molecular weight. Exposure of the oligocyclobutane to vacuum in the presence of the pyridine(diimine) iron precatalyst used to synthesize it resulted in deoligomerization to generate pristine butadiene, demonstrating a rare example of closed-loop chemical recycling of an oligomeric material derived from a commodity hydrocarbon feedstock. Iron-catalysed [2+2] cycloaddition/oligomerization of neat butadiene affords (1,n′-divinyl)oligocyclobutane—a telechelic, crystalline material consisting of 1,3-enchained cyclobutyl units. This oligocyclobutane can be chemically recycled to pure butadiene using the same iron catalyst employed in its synthesis, demonstrating design principles for next-generation plastic materials that can be returned to pristine monomer.
Databáze: OpenAIRE
Externí odkaz: