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Biobased aliphatic polyesters from a spirocyclic dicarboxylate monomer derived from levulinic acid

Valsange, Nitin LU ; Warlin, Niklas LU ; Mankar, Smita LU ; Rehnberg, Nicola LU orcid ; Lundmark, Stefan ; Zhang, Baozhong LU and Jannasch, Patric LU orcid (2021) In Green Chemistry 23(15). p.5706-5723
Abstract
Levulinic acid derived from lignocellulose is an important biobased building block chemical. Here, we report on the synthesis and polymerization of a rigid spirocyclic diester monomer to produce polyesters and copolyesters. The monomer was prepared via a one-step acid catalyzed ketalization involving ethyl levulinate and pentaerythritol by employing a straightforward, solvent-free, and readily scalable method which required no chromatographic purification. Still, careful removal of traces of water from the spirodiester prior to the polycondensations proved crucial to avoid side reactions. A preliminary life cycle assessment (LCA) in terms of greenhouse gas (GHG) emissions indicated that the corresponding spirodiacid tended to be... (More)
Levulinic acid derived from lignocellulose is an important biobased building block chemical. Here, we report on the synthesis and polymerization of a rigid spirocyclic diester monomer to produce polyesters and copolyesters. The monomer was prepared via a one-step acid catalyzed ketalization involving ethyl levulinate and pentaerythritol by employing a straightforward, solvent-free, and readily scalable method which required no chromatographic purification. Still, careful removal of traces of water from the spirodiester prior to the polycondensations proved crucial to avoid side reactions. A preliminary life cycle assessment (LCA) in terms of greenhouse gas (GHG) emissions indicated that the corresponding spirodiacid tended to be environmentally favourable, producing less CO2 emission than e.g., biobased succinic acid and adipic acid. A series of aliphatic polyesters with reasonably high molecular weights was subsequently prepared in melt and modified melt polycondensations of the spiro-diester with 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,4-cyclohexanedimethanol, respectively. The resulting fully amorphous polyesters showed glass transition temperatures (Tgs) in the range 12-49 °C and thermal
stability up to 300 °C. Hot-pressed films of the polyesters based on neopentyl glycol and 1,4-cyclohexanedimethanol were transparent and mechanically strong, and dynamic melt rheology showed stable shear moduli over time to indicate good processability. In addition, the spiro-diester monomer was employed in copolycondensations with diethyl adipate and 1,4-butanediol and demonstrated good reactivity and stability. Hence, the results of the present study indicate that the spiro-diester based on levulinic acid is an effective monomer for the preparation of aliphatic polyesters and other condensation polymers.
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author
; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Green Chemistry
volume
23
issue
15
pages
18 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85112370639
ISSN
1463-9270
DOI
10.1039/D1GC00724F
project
STEPS – Sustainable Plastics and Transition Pathways, Phase 2
language
English
LU publication?
yes
id
c0b9a79b-dc61-4305-8048-4d5c69d35235
date added to LUP
2020-11-29 20:39:49
date last changed
2022-04-26 22:15:44
@article{c0b9a79b-dc61-4305-8048-4d5c69d35235,
  abstract     = {{Levulinic acid derived from lignocellulose is an important biobased building block chemical. Here, we report on the synthesis and polymerization of a rigid spirocyclic diester monomer to produce polyesters and copolyesters. The monomer was prepared via a one-step acid catalyzed ketalization involving ethyl levulinate and pentaerythritol by employing a straightforward, solvent-free, and readily scalable method which required no chromatographic purification. Still, careful removal of traces of water from the spirodiester prior to the polycondensations proved crucial to avoid side reactions. A preliminary life cycle assessment (LCA) in terms of greenhouse gas (GHG) emissions indicated that the corresponding spirodiacid tended to be environmentally favourable, producing less CO<sub>2</sub> emission than e.g., biobased succinic acid and adipic acid. A series of aliphatic polyesters with reasonably high molecular weights was subsequently prepared in melt and modified melt polycondensations of the spiro-diester with 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,4-cyclohexanedimethanol, respectively. The resulting fully amorphous polyesters showed glass transition temperatures (<i>T</i><sub>g</sub>s) in the range 12-49 °C and thermal<br/>stability up to 300 °C. Hot-pressed films of the polyesters based on neopentyl glycol and 1,4-cyclohexanedimethanol were transparent and mechanically strong, and dynamic melt rheology showed stable shear moduli over time to indicate good processability. In addition, the spiro-diester monomer was employed in copolycondensations with diethyl adipate and 1,4-butanediol and demonstrated good reactivity and stability. Hence, the results of the present study indicate that the spiro-diester based on levulinic acid is an effective monomer for the preparation of aliphatic polyesters and other condensation polymers.<br/>}},
  author       = {{Valsange, Nitin and Warlin, Niklas and Mankar, Smita and Rehnberg, Nicola and Lundmark, Stefan and Zhang, Baozhong and Jannasch, Patric}},
  issn         = {{1463-9270}},
  language     = {{eng}},
  number       = {{15}},
  pages        = {{5706--5723}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Green Chemistry}},
  title        = {{Biobased aliphatic polyesters from a spirocyclic dicarboxylate monomer derived from levulinic acid}},
  url          = {{http://dx.doi.org/10.1039/D1GC00724F}},
  doi          = {{10.1039/D1GC00724F}},
  volume       = {{23}},
  year         = {{2021}},
}