Covalent Adaptable Polymethacrylate Networks by Hydrazide Crosslinking Via Isosorbide Levulinate Side Groups
Matt, Livia ; Sedrik, Rauno ; Bonjour, Olivier LU ; Vasiliauskaité, Miglé ; Jannasch, Patric LU
and Vares, Lauri
(2023)
In ACS Sustainable Chemistry & Engineering
11(22).
p.8294-8307
- Abstract
- Reversible crosslinking offers an attractive strategy to modify and improve the properties of polymer materials while concurrently enabling a pathway for chemical recycling. This can, for example, be achieved by incorporating a ketone functionality into the polymer structure to enable post-polymerization crosslinking with dihydrazides. The resulting covalent adaptable network contains acylhydrazone bonds cleavable under acidic conditions, thereby providing reversibility. In the present work, we regioselectively prepare a novel isosorbide monomethacrylate with a pendant levulinoyl group via a two-step biocatalytic synthesis. Subsequently, a series of copolymers with different contents of the levulinic isosorbide monomer and methyl... (More)
- Reversible crosslinking offers an attractive strategy to modify and improve the properties of polymer materials while concurrently enabling a pathway for chemical recycling. This can, for example, be achieved by incorporating a ketone functionality into the polymer structure to enable post-polymerization crosslinking with dihydrazides. The resulting covalent adaptable network contains acylhydrazone bonds cleavable under acidic conditions, thereby providing reversibility. In the present work, we regioselectively prepare a novel isosorbide monomethacrylate with a pendant levulinoyl group via a two-step biocatalytic synthesis. Subsequently, a series of copolymers with different contents of the levulinic isosorbide monomer and methyl methacrylate are prepared by radical polymerization. Using dihydrazides, these linear copolymers are then crosslinked via reaction with the ketone groups in the levulinic side chains. Compared to the linear prepolymers, the crosslinked networks exhibit enhanced glass transition temperatures and thermal stability, up to 170 and 286 °C, respectively. Moreover, the dynamic covalent acylhydrazone bonds are efficiently and selectively cleaved under acidic conditions to retrieve the linear polymethacrylates. We next show that recovered polymers can again be crosslinked with adipic dihydrazide, thus demonstrating the circularity of the materials. Consequently, we envision that these novel levulinic isosorbide-based dynamic polymethacrylate networks have great potential in the field of recyclable and reusable biobased thermoset polymers. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/94e46ef8-e6eb-409a-97e9-c6be23bf3ca1
- author
- Matt, Livia
; Sedrik, Rauno
; Bonjour, Olivier
LU
; Vasiliauskaité, Miglé
; Jannasch, Patric
LU
and Vares, Lauri
- organization
- publishing date
- 2023
- type
- Contribution to journal
- publication status
- published
- subject
- in
- ACS Sustainable Chemistry & Engineering
- volume
- 11
- issue
- 22
- pages
- 8294 - 8307
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- scopus:85162776814
- pmid:37292449
- ISSN
- 2168-0485
- DOI
- 10.1021/acssuschemeng.3c00747
- language
- English
- LU publication?
- yes
- id
- 94e46ef8-e6eb-409a-97e9-c6be23bf3ca1
- date added to LUP
- 2023-02-08 10:26:15
- date last changed
- 2023-08-20 03:00:02
@article{94e46ef8-e6eb-409a-97e9-c6be23bf3ca1,
abstract = {{Reversible crosslinking offers an attractive strategy to modify and improve the properties of polymer materials while concurrently enabling a pathway for chemical recycling. This can, for example, be achieved by incorporating a ketone functionality into the polymer structure to enable post-polymerization crosslinking with dihydrazides. The resulting covalent adaptable network contains acylhydrazone bonds cleavable under acidic conditions, thereby providing reversibility. In the present work, we regioselectively prepare a novel isosorbide monomethacrylate with a pendant levulinoyl group via a two-step biocatalytic synthesis. Subsequently, a series of copolymers with different contents of the levulinic isosorbide monomer and methyl methacrylate are prepared by radical polymerization. Using dihydrazides, these linear copolymers are then crosslinked via reaction with the ketone groups in the levulinic side chains. Compared to the linear prepolymers, the crosslinked networks exhibit enhanced glass transition temperatures and thermal stability, up to 170 and 286 °C, respectively. Moreover, the dynamic covalent acylhydrazone bonds are efficiently and selectively cleaved under acidic conditions to retrieve the linear polymethacrylates. We next show that recovered polymers can again be crosslinked with adipic dihydrazide, thus demonstrating the circularity of the materials. Consequently, we envision that these novel levulinic isosorbide-based dynamic polymethacrylate networks have great potential in the field of recyclable and reusable biobased thermoset polymers.}},
author = {{Matt, Livia and Sedrik, Rauno and Bonjour, Olivier and Vasiliauskaité, Miglé and Jannasch, Patric and Vares, Lauri}},
issn = {{2168-0485}},
language = {{eng}},
number = {{22}},
pages = {{8294--8307}},
publisher = {{The American Chemical Society (ACS)}},
series = {{ACS Sustainable Chemistry & Engineering}},
title = {{Covalent Adaptable Polymethacrylate Networks by Hydrazide Crosslinking Via Isosorbide Levulinate Side Groups}},
url = {{http://dx.doi.org/10.1021/acssuschemeng.3c00747}},
doi = {{10.1021/acssuschemeng.3c00747}},
volume = {{11}},
year = {{2023}},
}