Enzymatic synthesis and polymerization of isosorbide-based monomethacrylates for high-Tg plastics
Matt, Livia ; Parve, Jaan ; Parve, Omar ; Pehk, Tõnis ; Pham, Thanh Huong LU ; Liblikas, Ilme ; Vares, Lauri and Jannasch, Patric LU
(2018)
In ACS Sustainable Chemistry & Engineering
6(12).
p.17382-17390
- Abstract
- Isosorbide is a stiff bicyclic diol derived from glycose-based polysaccharides, and is thus an attractive building block for novel rigid bioplastics. In the present work a highly regioselective biocatalytic approach for the synthesis of isosorbide 5-methacrylate was developed. The Lipozyme RM IM (Rhizomucor miehei lipase) catalyzed process is straightforward, easily scalable and chromatography-free; a simple extractive workup afforded the monomer at >99% purity and in 87% yield. The developed strategy was applied for the synthesis of a series of monomethacrylated isosorbide derivatives. Radical polymerization of the monomers produced rigid polymethacrylates with a certain side group in either endo or exo configuration, exclusively,... (More)
- Isosorbide is a stiff bicyclic diol derived from glycose-based polysaccharides, and is thus an attractive building block for novel rigid bioplastics. In the present work a highly regioselective biocatalytic approach for the synthesis of isosorbide 5-methacrylate was developed. The Lipozyme RM IM (Rhizomucor miehei lipase) catalyzed process is straightforward, easily scalable and chromatography-free; a simple extractive workup afforded the monomer at >99% purity and in 87% yield. The developed strategy was applied for the synthesis of a series of monomethacrylated isosorbide derivatives. Radical polymerization of the monomers produced rigid polymethacrylates with a certain side group in either endo or exo configuration, exclusively, which generated materials with great diversity of properties. For example, the two regioisomeric polymers carrying hydroxyl groups reached a glass transition temperature at Tg = 167 °C. The polymer tethered with dodecanoate chains in exo position showed crystallinity with an unexpectedly high melting point at Tm = 83 °C. In contrast, the corresponding sample with dodecanoate chains in endo positions was fully amorphous with Tg = 54 °C. Efficient biocatalytic synthesis combined with attractive polymer properties opens up possibilities for production of these bio-based polymers on an industrial scale. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/6ba8c1c4-4848-4ace-ab03-2cf46d17fe4b
- author
- Matt, Livia
; Parve, Jaan
; Parve, Omar
; Pehk, Tõnis
; Pham, Thanh Huong
LU
; Liblikas, Ilme
; Vares, Lauri
and Jannasch, Patric
LU
- organization
- publishing date
- 2018
- type
- Contribution to journal
- publication status
- published
- subject
- in
- ACS Sustainable Chemistry & Engineering
- volume
- 6
- issue
- 12
- pages
- 9 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- scopus:85057589821
- ISSN
- 2168-0485
- DOI
- 10.1021/acssuschemeng.8b05074
- language
- English
- LU publication?
- yes
- additional info
- Publication Date (Web): November 12, 2018
- id
- 6ba8c1c4-4848-4ace-ab03-2cf46d17fe4b
- date added to LUP
- 2018-11-12 23:48:51
- date last changed
- 2022-03-17 19:02:36
@article{6ba8c1c4-4848-4ace-ab03-2cf46d17fe4b,
abstract = {{Isosorbide is a stiff bicyclic diol derived from glycose-based polysaccharides, and is thus an attractive building block for novel rigid bioplastics. In the present work a highly regioselective biocatalytic approach for the synthesis of isosorbide 5-methacrylate was developed. The Lipozyme RM IM (Rhizomucor miehei lipase) catalyzed process is straightforward, easily scalable and chromatography-free; a simple extractive workup afforded the monomer at >99% purity and in 87% yield. The developed strategy was applied for the synthesis of a series of monomethacrylated isosorbide derivatives. Radical polymerization of the monomers produced rigid polymethacrylates with a certain side group in either endo or exo configuration, exclusively, which generated materials with great diversity of properties. For example, the two regioisomeric polymers carrying hydroxyl groups reached a glass transition temperature at <i>T</i><sub>g</sub> = 167 °C. The polymer tethered with dodecanoate chains in exo position showed crystallinity with an unexpectedly high melting point at <i>T</i><sub>m</sub> = 83 °C. In contrast, the corresponding sample with dodecanoate chains in endo positions was fully amorphous with <i>T</i><sub>g</sub> = 54 °C. Efficient biocatalytic synthesis combined with attractive polymer properties opens up possibilities for production of these bio-based polymers on an industrial scale.}},
author = {{Matt, Livia and Parve, Jaan and Parve, Omar and Pehk, Tõnis and Pham, Thanh Huong and Liblikas, Ilme and Vares, Lauri and Jannasch, Patric}},
issn = {{2168-0485}},
language = {{eng}},
number = {{12}},
pages = {{17382--17390}},
publisher = {{The American Chemical Society (ACS)}},
series = {{ACS Sustainable Chemistry & Engineering}},
title = {{Enzymatic synthesis and polymerization of isosorbide-based monomethacrylates for high-<i>T</i><sub>g</sub> plastics}},
url = {{http://dx.doi.org/10.1021/acssuschemeng.8b05074}},
doi = {{10.1021/acssuschemeng.8b05074}},
volume = {{6}},
year = {{2018}},
}