Effective strategy for high-yield furan dicarboxylate production for biobased polyester applications

Minjune Kim, Yaqiong Su, T. Aoshima, A. (Atsushi) Fukuoka, Emiel Hensen (Corresponding author), Kiyotaka Nakajima (Corresponding author)

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1 Citation (Scopus)
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Abstract

A unique strategy for the formation of furan-2,5-dicarboxylic acid (FDCA)-derived esters with methanol and ethylene glycol in concentrated solutions was reported using a six-membered ring acetal of (5-hydroxymethyl)furfural (HMF) with 1,3-propanediol in order to improve the economics for the production of polyethylene 2,5-furandicarboxylate (PEF), a biobased polyester. Aerobic oxidative esterification with methanol and ethylene glycol in the presence of a CeO 2 -supported Au catalyst gave 80-95% yields of methyl furan-2,5-dicarboxylate and bis(2-hydroxyethyl)furan-2,5-dicarboxylate from concentrated HMF-acetal solutions (10-20 wt %). Kinetic studies combined with density functional theory (DFT) calculations were used to identify two key steps for the conversion of the cyclic acetal ring to the corresponding methyl ester: (i) partial hydrolysis of the acetal ring by OH - ions and (ii) subsequent oxidation of the hemiacetal in solution by molecular O 2 on Au nanoparticles. These results represent a significant contribution not only to cutting-edge conversion technology for renewable biomass feedstocks to PEF-based applications but also to opportunities for the efficient conversion of substrates with a reactive formyl group in high yield.

Original languageEnglish
Pages (from-to)4277-4285
Number of pages9
JournalACS Catalysis
Volume9
Issue number5
DOIs
Publication statusPublished - 3 May 2019

Fingerprint

Acetals
Polyesters
Furfural
Ethylene glycol
Ethylene Glycol
Polyethylenes
Esters
Polyethylene
Methanol
Esterification
Catalyst supports
Dicarboxylic Acids
Feedstocks
Density functional theory
Hydrolysis
Biomass
Nanoparticles
Oxidation
Economics
Kinetics

Keywords

  • acetal functionality
  • biobased polymer
  • biomass conversion
  • oxidative esterification
  • supported Au catalyst

Cite this

Kim, Minjune ; Su, Yaqiong ; Aoshima, T. ; Fukuoka, A. (Atsushi) ; Hensen, Emiel ; Nakajima, Kiyotaka. / Effective strategy for high-yield furan dicarboxylate production for biobased polyester applications. In: ACS Catalysis. 2019 ; Vol. 9, No. 5. pp. 4277-4285.
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abstract = "A unique strategy for the formation of furan-2,5-dicarboxylic acid (FDCA)-derived esters with methanol and ethylene glycol in concentrated solutions was reported using a six-membered ring acetal of (5-hydroxymethyl)furfural (HMF) with 1,3-propanediol in order to improve the economics for the production of polyethylene 2,5-furandicarboxylate (PEF), a biobased polyester. Aerobic oxidative esterification with methanol and ethylene glycol in the presence of a CeO 2 -supported Au catalyst gave 80-95{\%} yields of methyl furan-2,5-dicarboxylate and bis(2-hydroxyethyl)furan-2,5-dicarboxylate from concentrated HMF-acetal solutions (10-20 wt {\%}). Kinetic studies combined with density functional theory (DFT) calculations were used to identify two key steps for the conversion of the cyclic acetal ring to the corresponding methyl ester: (i) partial hydrolysis of the acetal ring by OH - ions and (ii) subsequent oxidation of the hemiacetal in solution by molecular O 2 on Au nanoparticles. These results represent a significant contribution not only to cutting-edge conversion technology for renewable biomass feedstocks to PEF-based applications but also to opportunities for the efficient conversion of substrates with a reactive formyl group in high yield.",
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Effective strategy for high-yield furan dicarboxylate production for biobased polyester applications. / Kim, Minjune; Su, Yaqiong; Aoshima, T.; Fukuoka, A. (Atsushi); Hensen, Emiel (Corresponding author); Nakajima, Kiyotaka (Corresponding author).

In: ACS Catalysis, Vol. 9, No. 5, 03.05.2019, p. 4277-4285.

Research output: Contribution to journalArticleAcademicpeer-review

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