Carbon Dioxide Copolymerization Study with a Sterically Encumbering Naphthalene-Derived Oxide Academic Article

abstract

• 2015 American Chemical Society. Poly(1,4-dihydronaphthalene carbonate) has been prepared via the catalytic coupling of carbon dioxide and 1,4-dihydronaphthalene oxide using chromium(III) catalysts. The copolymer formation is found to be greatly dependent on the steric environment around the metal center. Traditional (salen)Cr^IIIX/cocatalyst systems bearing bulky t-butyl groups hinder the approach of the large monomer, significantly diminishing polymer chain growth and providing the entropically favored cyclic byproduct in excess. In contrast, employing the sterically unencumbered azaannulene-derived catalyst, (tmtaa)Cr^IIIX/cocatalyst system (tmtaa = tetramethyltetraazaannulene) shows polymer selectivity close to 90% with three times the activity (TOF = 20-30 h^-1). With the use of a bifunctional (salen)Cr^III catalyst, even higher polymer selectivity (>90%) can be observed. The complete synthesis of a new bifunctional tetraazaannulene ligand for a more effective catalyst is also described herein.

authors

• Darensbourg, Donald

published proceedings

• ACS CATALYSIS

altmetric score

• 3.35

author list (cited authors)

• Darensbourg, D. J., & Kyran, S. J.

citation count

• 17

complete list of authors

• Darensbourg, Donald J||Kyran, Samuel J

publication date

• September 2015

publisher

• American Chemical Society (ACS)  Publisher

published in

• ACS Catalysis  Journal

keywords

• 1,4-dihydronaphthalene Oxide
• Carbon Dioxide
• Copolymerization
• Polycarbonate
• Steric Effect

Digital Object Identifier (DOI)

• 10.1021/acscatal.5b01375

start page

• 5421

end page

• 5430

volume

• 5

issue

• 9

URL

• http%3A%2F%2Fdx.doi.org%2F10.1021%2Facscatal.5b01375