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A “Transient-Comonomer” Strategy for Polycondensation of Lignin-Derived AB-Type Aromatic Polyesters to High Molecular Weight

Nguyen, Tam T. LU ; Ben Youssef, Ismail ; Sarbandi, Reza ; De Smedt, Tom ; Jannasch, Patric LU orcid and Zhang, Baozhong LU (2026) In European Polymer Journal
Abstract
In the active exploration of novel biobased semicrystalline polyesters
to replace petrochemical plastics, AB-type aromatic condensation
polymerization is relatively rarely investigated but gains growing
attention due to the straightforward synthesis of AB-type monomers from
diverse asymmetric biobased feedstocks. However, achieving high
molecular weights through AB-type melt polycondensations is often
challenging due to premature crystallization and limited thermal
stability of the bio-based monomers. Herein, we investigate the
polycondensation of methyl 4-(2-hydroxyethoxy)benzoate (MEB), a biobased
aromatic hydroxy-ester monomer (AB-type), via the classical two-stage
melt... (More)
In the active exploration of novel biobased semicrystalline polyesters
to replace petrochemical plastics, AB-type aromatic condensation
polymerization is relatively rarely investigated but gains growing
attention due to the straightforward synthesis of AB-type monomers from
diverse asymmetric biobased feedstocks. However, achieving high
molecular weights through AB-type melt polycondensations is often
challenging due to premature crystallization and limited thermal
stability of the bio-based monomers. Herein, we investigate the
polycondensation of methyl 4-(2-hydroxyethoxy)benzoate (MEB), a biobased
aromatic hydroxy-ester monomer (AB-type), via the classical two-stage
melt transesterification polycondensation process. We demonstrate an
efficient “transient-comonomers” strategy to enhance the molecular
weight of PEB up to 1.15 dL g−1 by adding a small amount of
aliphatic AA/BB-type comonomer pair at the beginning of polymerization.
These comonomers suppress premature solidification during the initial
stages of melt polycondensation and are partially depleted during the
later stages of the reaction. In addition, we also investigated the
effects of various metal-based catalysts, including a kinetic analysis
of the transesterification steps, which revealed that titanium-based
catalysts exhibited a faster reaction rate compared to other catalysts
based on antimony, tin, manganese, and zinc. Furthermore, the catalyst
also influenced the thermal properties of the resulting polyester,
particularly the crystallinity and crystallization kinetics. Overall,
this study provides new insights into achieving high-molecular-weight
biobased aromatic polyesters via AB-type polycondensation and offers a
promising approach for broadening the synthesis approaches for
sustainable condensation polymers. (Less)
Please use this url to cite or link to this publication:
author
; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
epub
subject
in
European Polymer Journal
article number
114564
publisher
Elsevier
ISSN
0014-3057
DOI
10.1016/j.eurpolymj.2026.114564
language
English
LU publication?
yes
id
d3b432e0-00bc-45c1-808d-044d1637f6ab
date added to LUP
2025-12-04 11:25:56
date last changed
2026-02-10 15:00:40
@article{d3b432e0-00bc-45c1-808d-044d1637f6ab,
  abstract     = {{In the active exploration of novel biobased semicrystalline polyesters <br>
to replace petrochemical plastics, AB-type aromatic condensation <br>
polymerization is relatively rarely investigated but gains growing <br>
attention due to the straightforward synthesis of AB-type monomers from <br>
diverse asymmetric biobased feedstocks. However, achieving high <br>
molecular weights through AB-type melt polycondensations is often <br>
challenging due to premature crystallization and limited thermal <br>
stability of the bio-based monomers. Herein, we investigate the <br>
polycondensation of methyl 4-(2-hydroxyethoxy)benzoate (MEB), a biobased<br>
 aromatic hydroxy-ester monomer (AB-type), via the classical two-stage <br>
melt transesterification polycondensation process. We demonstrate an <br>
efficient “transient-comonomers” strategy to enhance the molecular <br>
weight of PEB up to 1.15 dL g<sup>−1</sup> by adding a small amount of <br>
aliphatic AA/BB-type comonomer pair at the beginning of polymerization. <br>
These comonomers suppress premature solidification during the initial <br>
stages of melt polycondensation and are partially depleted during the <br>
later stages of the reaction. In addition, we also investigated the <br>
effects of various metal-based catalysts, including a kinetic analysis <br>
of the transesterification steps, which revealed that titanium-based <br>
catalysts exhibited a faster reaction rate compared to other catalysts <br>
based on antimony, tin, manganese, and zinc. Furthermore, the catalyst <br>
also influenced the thermal properties of the resulting polyester, <br>
particularly the crystallinity and crystallization kinetics. Overall, <br>
this study provides new insights into achieving high-molecular-weight <br>
biobased aromatic polyesters via AB-type polycondensation and offers a <br>
promising approach for broadening the synthesis approaches for <br>
sustainable condensation polymers.}},
  author       = {{Nguyen, Tam T. and Ben Youssef, Ismail and Sarbandi, Reza and De Smedt, Tom and Jannasch, Patric and Zhang, Baozhong}},
  issn         = {{0014-3057}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{European Polymer Journal}},
  title        = {{A “Transient-Comonomer” Strategy for Polycondensation of Lignin-Derived AB-Type Aromatic Polyesters to High Molecular Weight}},
  url          = {{http://dx.doi.org/10.1016/j.eurpolymj.2026.114564}},
  doi          = {{10.1016/j.eurpolymj.2026.114564}},
  year         = {{2026}},
}