Enzymatic synthesis and characterization of novel terpolymers from renewable sources

Diana Aparaschivei, Anamaria Todea*, August E. Frissen, Valentin Badea, Gerlinde Rusu, Eugen Sisu, Maria Puiu, Carmen G. Boeriu, Francisc Peter

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

2,5-Furandicarboxylic acid and itaconic acid are both important biobased platform chemicals and their terpolymer with 1,6-hexanediol (HDO) can be the starting point for a new class of reactive polyesters, with important applications. The green synthetic route developed in this study involves a biocatalytic condensation polymerization reaction of dimethyl furan-2,5-dicarboxylate (DMFDC) and dimethyl itaconate (DMI) with HDO in toluene at 80°C, using commercial immobilized lipases from Candida antarctica B. In the best conditions, the formed polymer product was isolated with more than 80% yield, containing about 85% terpolymer with average molecular mass of about 1200 (Mn, calculated from MALDI-TOF MS data) and 15% DMFDC-HDO copolymer. Considering the higher reactivity of DMFDC, the composition of the synthesized polymer can be directed by adjusting the molar ratio of DMFDC and DMI, as well as by extending the reaction time. Structural analysis by NMR demonstrated the regioselective preference for the carbonyl group from DMI adjacent to the methylene group. The biocatalyst was successfully reused in multiple reaction cycles.

Original languageEnglish
JournalPure and Applied Chemistry
Volume91
Issue number3
Early online date22 Nov 2018
DOIs
Publication statusPublished - 22 Nov 2018

Fingerprint

Terpolymers
Biocatalysts
Acids
Candida
Lipases
Molecular mass
Polymers
Polycondensation
Structural analysis
Toluene
Polyesters
Copolymers
Nuclear magnetic resonance
Chemical analysis
furan
Enzymes
dimethyl itaconate

Keywords

  • biobased terpolymer
  • biocatalysis
  • dimethyl furan-2,5-dicarboxylate
  • dimethyl itaconate
  • lipase
  • POC-2018

Cite this

Aparaschivei, Diana ; Todea, Anamaria ; Frissen, August E. ; Badea, Valentin ; Rusu, Gerlinde ; Sisu, Eugen ; Puiu, Maria ; Boeriu, Carmen G. ; Peter, Francisc. / Enzymatic synthesis and characterization of novel terpolymers from renewable sources. In: Pure and Applied Chemistry. 2018 ; Vol. 91, No. 3.
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abstract = "2,5-Furandicarboxylic acid and itaconic acid are both important biobased platform chemicals and their terpolymer with 1,6-hexanediol (HDO) can be the starting point for a new class of reactive polyesters, with important applications. The green synthetic route developed in this study involves a biocatalytic condensation polymerization reaction of dimethyl furan-2,5-dicarboxylate (DMFDC) and dimethyl itaconate (DMI) with HDO in toluene at 80°C, using commercial immobilized lipases from Candida antarctica B. In the best conditions, the formed polymer product was isolated with more than 80{\%} yield, containing about 85{\%} terpolymer with average molecular mass of about 1200 (Mn, calculated from MALDI-TOF MS data) and 15{\%} DMFDC-HDO copolymer. Considering the higher reactivity of DMFDC, the composition of the synthesized polymer can be directed by adjusting the molar ratio of DMFDC and DMI, as well as by extending the reaction time. Structural analysis by NMR demonstrated the regioselective preference for the carbonyl group from DMI adjacent to the methylene group. The biocatalyst was successfully reused in multiple reaction cycles.",
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Enzymatic synthesis and characterization of novel terpolymers from renewable sources. / Aparaschivei, Diana; Todea, Anamaria; Frissen, August E.; Badea, Valentin; Rusu, Gerlinde; Sisu, Eugen; Puiu, Maria; Boeriu, Carmen G.; Peter, Francisc.

In: Pure and Applied Chemistry, Vol. 91, No. 3, 22.11.2018.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Enzymatic synthesis and characterization of novel terpolymers from renewable sources

AU - Aparaschivei, Diana

AU - Todea, Anamaria

AU - Frissen, August E.

AU - Badea, Valentin

AU - Rusu, Gerlinde

AU - Sisu, Eugen

AU - Puiu, Maria

AU - Boeriu, Carmen G.

AU - Peter, Francisc

PY - 2018/11/22

Y1 - 2018/11/22

N2 - 2,5-Furandicarboxylic acid and itaconic acid are both important biobased platform chemicals and their terpolymer with 1,6-hexanediol (HDO) can be the starting point for a new class of reactive polyesters, with important applications. The green synthetic route developed in this study involves a biocatalytic condensation polymerization reaction of dimethyl furan-2,5-dicarboxylate (DMFDC) and dimethyl itaconate (DMI) with HDO in toluene at 80°C, using commercial immobilized lipases from Candida antarctica B. In the best conditions, the formed polymer product was isolated with more than 80% yield, containing about 85% terpolymer with average molecular mass of about 1200 (Mn, calculated from MALDI-TOF MS data) and 15% DMFDC-HDO copolymer. Considering the higher reactivity of DMFDC, the composition of the synthesized polymer can be directed by adjusting the molar ratio of DMFDC and DMI, as well as by extending the reaction time. Structural analysis by NMR demonstrated the regioselective preference for the carbonyl group from DMI adjacent to the methylene group. The biocatalyst was successfully reused in multiple reaction cycles.

AB - 2,5-Furandicarboxylic acid and itaconic acid are both important biobased platform chemicals and their terpolymer with 1,6-hexanediol (HDO) can be the starting point for a new class of reactive polyesters, with important applications. The green synthetic route developed in this study involves a biocatalytic condensation polymerization reaction of dimethyl furan-2,5-dicarboxylate (DMFDC) and dimethyl itaconate (DMI) with HDO in toluene at 80°C, using commercial immobilized lipases from Candida antarctica B. In the best conditions, the formed polymer product was isolated with more than 80% yield, containing about 85% terpolymer with average molecular mass of about 1200 (Mn, calculated from MALDI-TOF MS data) and 15% DMFDC-HDO copolymer. Considering the higher reactivity of DMFDC, the composition of the synthesized polymer can be directed by adjusting the molar ratio of DMFDC and DMI, as well as by extending the reaction time. Structural analysis by NMR demonstrated the regioselective preference for the carbonyl group from DMI adjacent to the methylene group. The biocatalyst was successfully reused in multiple reaction cycles.

KW - biobased terpolymer

KW - biocatalysis

KW - dimethyl furan-2,5-dicarboxylate

KW - dimethyl itaconate

KW - lipase

KW - POC-2018

U2 - 10.1515/pac-2018-1015

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JO - Pure and Applied Chemistry

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SN - 0033-4545

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