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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)
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author
organization
publishing date
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
external identifiers
  • scopus:85057589821
  • scopus:85057529440
ISSN
2168-0485
DOI
10.1021/acssuschemeng.8b05074
language
English
LU publication?
yes
id
6ba8c1c4-4848-4ace-ab03-2cf46d17fe4b
date added to LUP
2018-11-12 23:48:51
date last changed
2019-02-20 11:35:21
@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 &gt;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},
  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},
  volume       = {6},
  year         = {2018},
}