Closed-loop chemically recyclable aromatic polyesters using asymmetric dicarboxylates obtainable from lignocellulose
(2025) In Green Chemistry 27(20). p.5770-5781- Abstract
- Utilizing building blocks derived from lignocellulose is an attractive strategy towards biobased aromatic polyesters. Here, we present the straightforward synthesis of three new asymmetric di-aromatic diester monomers by one-step reactions of lignin-derived hydroxybenzoates (methyl paraben, methyl vanillate and methyl syringate, respectively) with potentially sugar-based methyl 5-chloromethyl-2-furoate. The two diester monomers based on methyl paraben and methyl vanillate were polymerized with 1,6-hexanediol, 1,4-butanediol, and neopentyl glycol, respectively, to produce two series of polyesters with reasonably high molecular weights (12-37 kg mol−1). The fully amorphous polyesters showed high thermal stability... (More)
- Utilizing building blocks derived from lignocellulose is an attractive strategy towards biobased aromatic polyesters. Here, we present the straightforward synthesis of three new asymmetric di-aromatic diester monomers by one-step reactions of lignin-derived hydroxybenzoates (methyl paraben, methyl vanillate and methyl syringate, respectively) with potentially sugar-based methyl 5-chloromethyl-2-furoate. The two diester monomers based on methyl paraben and methyl vanillate were polymerized with 1,6-hexanediol, 1,4-butanediol, and neopentyl glycol, respectively, to produce two series of polyesters with reasonably high molecular weights (12-37 kg mol−1). The fully amorphous polyesters showed high thermal stability (Td,5 > 275 °C), tunable glass transition temperature (Tg ~ 36-75 °C), and moderately high mechanical stiffness. In addition, we have successfully developed and demonstrated a strategy for closed-loop chemical recycling of the polyesters through depolymerization using methanolysis, which allowed for the recovery of the native diester and diol monomers. The recovered monomers were subsequently repolymerized to produce a recycled polyester with properties comparable to the original one. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/d2d59384-65f7-44cd-aa65-28e9f7dc04fb
- author
- Valsange, Nitin G.
LU
; Warlin, Niklas
LU
; Mankar, Smita V.
LU
; Rehnberg, Nicola
LU
; Zhang, Baozhong LU and Jannasch, Patric LU
- organization
- publishing date
- 2025
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Green Chemistry
- volume
- 27
- issue
- 20
- pages
- 5770 - 5781
- publisher
- Royal Society of Chemistry
- external identifiers
-
- scopus:105003914635
- ISSN
- 1463-9270
- DOI
- 10.1039/D4GC05572A
- language
- English
- LU publication?
- yes
- additional info
- From the themed collection: Make polymers sustainable, why and how?
- id
- d2d59384-65f7-44cd-aa65-28e9f7dc04fb
- date added to LUP
- 2023-11-09 19:41:03
- date last changed
- 2025-05-21 09:20:24
@article{d2d59384-65f7-44cd-aa65-28e9f7dc04fb, abstract = {{Utilizing building blocks derived from lignocellulose is an attractive strategy towards biobased aromatic polyesters. Here, we present the straightforward synthesis of three new asymmetric di-aromatic diester monomers by one-step reactions of lignin-derived hydroxybenzoates (methyl paraben, methyl vanillate and methyl syringate, respectively) with potentially sugar-based methyl 5-chloromethyl-2-furoate. The two diester monomers based on methyl paraben and methyl vanillate were polymerized with 1,6-hexanediol, 1,4-butanediol, and neopentyl glycol, respectively, to produce two series of polyesters with reasonably high molecular weights (12-37 kg mol<sup>−1</sup>). The fully amorphous polyesters showed high thermal stability (<i>T</i><sub>d,5</sub> > 275 °C), tunable glass transition temperature (<i>T</i>g ~ 36-75 °C), and moderately high mechanical stiffness. In addition, we have successfully developed and demonstrated a strategy for closed-loop chemical recycling of the polyesters through depolymerization using methanolysis, which allowed for the recovery of the native diester and diol monomers. The recovered monomers were subsequently repolymerized to produce a recycled polyester with properties comparable to the original one.}}, author = {{Valsange, Nitin G. and Warlin, Niklas and Mankar, Smita V. and Rehnberg, Nicola and Zhang, Baozhong and Jannasch, Patric}}, issn = {{1463-9270}}, language = {{eng}}, number = {{20}}, pages = {{5770--5781}}, publisher = {{Royal Society of Chemistry}}, series = {{Green Chemistry}}, title = {{Closed-loop chemically recyclable aromatic polyesters using asymmetric dicarboxylates obtainable from lignocellulose}}, url = {{http://dx.doi.org/10.1039/D4GC05572A}}, doi = {{10.1039/D4GC05572A}}, volume = {{27}}, year = {{2025}}, }