TY - JOUR
T1 - Branched Diol Monomers from the Sequential Hydrogenation of Renewable Carboxylic Acids
AU - Spanjers, Charles S.
AU - Schneiderman, Deborah K.
AU - Wang, Jay Z.
AU - Wang, Jingyu
AU - Hillmyer, Marc A.
AU - Zhang, Kechun
AU - Dauenhauer, Paul J.
N1 - Publisher Copyright:
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/10/6
Y1 - 2016/10/6
N2 - A prominent challenge in replacing petrochemical polymers with bioderived alternatives is the efficient transformation of biomass into useful monomers. In this work, we demonstrate a practical process for the synthesis of multifunctional alcohols from five- and six-carbon acids using heterogeneous catalysts in aqueous media. Design of this process was guided by thermodynamic calculations, which indicate the need for two sequential high-pressure hydrogenations: one, reduction of the acid to a lactone at high temperature; two, further reduction of the lactone to the corresponding diol or triol at low temperature. For example, the conversion of mesaconic acid into (α or β)-methyl-γ-butyrolactone was achieved with 95 % selectivity at a turnover frequency of 1.2 min−1 over Pd/C at 240 °C. Subsequent conversion of (α or β)-methyl-γ-butyrolactone into 2-methyl-1,4-butanediol was achieved with a yield of 80 % with Ru/C at 100 °C. This process is an efficient method for the production of lactones, diols, and triols, all valuable monomers for the synthesis of bioderived branched polyesters.
AB - A prominent challenge in replacing petrochemical polymers with bioderived alternatives is the efficient transformation of biomass into useful monomers. In this work, we demonstrate a practical process for the synthesis of multifunctional alcohols from five- and six-carbon acids using heterogeneous catalysts in aqueous media. Design of this process was guided by thermodynamic calculations, which indicate the need for two sequential high-pressure hydrogenations: one, reduction of the acid to a lactone at high temperature; two, further reduction of the lactone to the corresponding diol or triol at low temperature. For example, the conversion of mesaconic acid into (α or β)-methyl-γ-butyrolactone was achieved with 95 % selectivity at a turnover frequency of 1.2 min−1 over Pd/C at 240 °C. Subsequent conversion of (α or β)-methyl-γ-butyrolactone into 2-methyl-1,4-butanediol was achieved with a yield of 80 % with Ru/C at 100 °C. This process is an efficient method for the production of lactones, diols, and triols, all valuable monomers for the synthesis of bioderived branched polyesters.
KW - biomass
KW - diols
KW - heterogeneous catalysis
KW - polymers
KW - sustainable chemistry
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U2 - 10.1002/cctc.201600710
DO - 10.1002/cctc.201600710
M3 - Article
AN - SCOPUS:84989836468
SN - 1867-3880
VL - 8
SP - 3031
EP - 3035
JO - ChemCatChem
JF - ChemCatChem
IS - 19
ER -