Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

Álvaro Cruz-Izquierdo, Lambertus A.M. van den Broek, Juan L. Serra, María J. Llama, Carmen G. Boeriu*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

15 Citations (Scopus)

Abstract

2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12, using immobilized lipase B from Candida antarctica (Novozym 435) in dry organic solvents. Dimethyl furan-2,5-dicarboxylic acid (A) and 1,4-butanediol (B) were used as model substrates under different conditions producing a mixture of cyclic (CEOs) and linear (LEOs) ester oligomers up to decamers and dodecamers, respectively, with high yield. The size of the oligomers and distribution of the products is controlled by the initial concentration of substrates and temperature. While the shortest CEOs are the main cyclic compounds at 20 mM, the longest CEOs are formed at 175 mM. The chain length of the aliphatic diol co-monomers strongly influences the yield and the type of oligoesters formed. High substrate conversion of 90-95% was obtained for C4-C12 diols, while in the case of ethylene glycol and 1,3-propanediol the conversion was moderate (i.e., 75%). The product of the reaction between dimethyl furan-2,5-dicarboxylate and ethylene glycol (C2) and 1,3-propanediol (C3), respectively, consisted only of linear oligoesters. Longer oligoesters were obtained for alkyl chains higher than C4. The chain length and the abundance of oligoesters increases in the order: C2<C12<C10<C3<C8<C4 <C6. No substrate or product inhibition was observed in the production of furan-based oligoesters. The present biobased oligoesters are obtained via a green process and have potential application as macromonomers.

Original languageEnglish
Pages (from-to)59-69
JournalPure and Applied Chemistry
Volume87
Issue number1
DOIs
Publication statusPublished - 2015

Fingerprint

Lipases
Lipase
Chain length
Acids
Substrates
Ethylene glycol
Oligomers
Ethylene Glycol
Candida
Dicarboxylic Acids
Organic solvents
Esters
Monomers
Polymers
2,5-furandicarboxylic acid
furan
Temperature
1,3-propanediol

Keywords

  • 2,5-furandicarboxylic acid
  • Bioplastics
  • Enzymatic polymerization
  • Lipase
  • Oligoesters
  • POC-2014

Cite this

@article{b2777c99f5a0444ca765e0a3da62dd24,
title = "Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols",
abstract = "2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12, using immobilized lipase B from Candida antarctica (Novozym 435) in dry organic solvents. Dimethyl furan-2,5-dicarboxylic acid (A) and 1,4-butanediol (B) were used as model substrates under different conditions producing a mixture of cyclic (CEOs) and linear (LEOs) ester oligomers up to decamers and dodecamers, respectively, with high yield. The size of the oligomers and distribution of the products is controlled by the initial concentration of substrates and temperature. While the shortest CEOs are the main cyclic compounds at 20 mM, the longest CEOs are formed at 175 mM. The chain length of the aliphatic diol co-monomers strongly influences the yield and the type of oligoesters formed. High substrate conversion of 90-95{\%} was obtained for C4-C12 diols, while in the case of ethylene glycol and 1,3-propanediol the conversion was moderate (i.e., 75{\%}). The product of the reaction between dimethyl furan-2,5-dicarboxylate and ethylene glycol (C2) and 1,3-propanediol (C3), respectively, consisted only of linear oligoesters. Longer oligoesters were obtained for alkyl chains higher than C4. The chain length and the abundance of oligoesters increases in the order: C2<C12<C10<C3<C8<C4 <C6. No substrate or product inhibition was observed in the production of furan-based oligoesters. The present biobased oligoesters are obtained via a green process and have potential application as macromonomers.",
keywords = "2,5-furandicarboxylic acid, Bioplastics, Enzymatic polymerization, Lipase, Oligoesters, POC-2014",
author = "{\'A}lvaro Cruz-Izquierdo and {van den Broek}, {Lambertus A.M.} and Serra, {Juan L.} and Llama, {Mar{\'i}a J.} and Boeriu, {Carmen G.}",
year = "2015",
doi = "10.1515/pac-2014-1003",
language = "English",
volume = "87",
pages = "59--69",
journal = "Pure and Applied Chemistry",
issn = "0033-4545",
publisher = "De Gruyter",
number = "1",

}

Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols. / Cruz-Izquierdo, Álvaro; van den Broek, Lambertus A.M.; Serra, Juan L.; Llama, María J.; Boeriu, Carmen G.

In: Pure and Applied Chemistry, Vol. 87, No. 1, 2015, p. 59-69.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

AU - Cruz-Izquierdo, Álvaro

AU - van den Broek, Lambertus A.M.

AU - Serra, Juan L.

AU - Llama, María J.

AU - Boeriu, Carmen G.

PY - 2015

Y1 - 2015

N2 - 2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12, using immobilized lipase B from Candida antarctica (Novozym 435) in dry organic solvents. Dimethyl furan-2,5-dicarboxylic acid (A) and 1,4-butanediol (B) were used as model substrates under different conditions producing a mixture of cyclic (CEOs) and linear (LEOs) ester oligomers up to decamers and dodecamers, respectively, with high yield. The size of the oligomers and distribution of the products is controlled by the initial concentration of substrates and temperature. While the shortest CEOs are the main cyclic compounds at 20 mM, the longest CEOs are formed at 175 mM. The chain length of the aliphatic diol co-monomers strongly influences the yield and the type of oligoesters formed. High substrate conversion of 90-95% was obtained for C4-C12 diols, while in the case of ethylene glycol and 1,3-propanediol the conversion was moderate (i.e., 75%). The product of the reaction between dimethyl furan-2,5-dicarboxylate and ethylene glycol (C2) and 1,3-propanediol (C3), respectively, consisted only of linear oligoesters. Longer oligoesters were obtained for alkyl chains higher than C4. The chain length and the abundance of oligoesters increases in the order: C2<C12<C10<C3<C8<C4 <C6. No substrate or product inhibition was observed in the production of furan-based oligoesters. The present biobased oligoesters are obtained via a green process and have potential application as macromonomers.

AB - 2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12, using immobilized lipase B from Candida antarctica (Novozym 435) in dry organic solvents. Dimethyl furan-2,5-dicarboxylic acid (A) and 1,4-butanediol (B) were used as model substrates under different conditions producing a mixture of cyclic (CEOs) and linear (LEOs) ester oligomers up to decamers and dodecamers, respectively, with high yield. The size of the oligomers and distribution of the products is controlled by the initial concentration of substrates and temperature. While the shortest CEOs are the main cyclic compounds at 20 mM, the longest CEOs are formed at 175 mM. The chain length of the aliphatic diol co-monomers strongly influences the yield and the type of oligoesters formed. High substrate conversion of 90-95% was obtained for C4-C12 diols, while in the case of ethylene glycol and 1,3-propanediol the conversion was moderate (i.e., 75%). The product of the reaction between dimethyl furan-2,5-dicarboxylate and ethylene glycol (C2) and 1,3-propanediol (C3), respectively, consisted only of linear oligoesters. Longer oligoesters were obtained for alkyl chains higher than C4. The chain length and the abundance of oligoesters increases in the order: C2<C12<C10<C3<C8<C4 <C6. No substrate or product inhibition was observed in the production of furan-based oligoesters. The present biobased oligoesters are obtained via a green process and have potential application as macromonomers.

KW - 2,5-furandicarboxylic acid

KW - Bioplastics

KW - Enzymatic polymerization

KW - Lipase

KW - Oligoesters

KW - POC-2014

U2 - 10.1515/pac-2014-1003

DO - 10.1515/pac-2014-1003

M3 - Article

VL - 87

SP - 59

EP - 69

JO - Pure and Applied Chemistry

JF - Pure and Applied Chemistry

SN - 0033-4545

IS - 1

ER -