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A rigid spirocyclic diol from fructose-based 5-hydroxymethylfurfural: synthesis, life-cycle assessment, and polymerization for renewable polyesters and poly(urethane-urea)s

Warlin, Niklas LU ; Garcia Gonzalez, Nelly LU ; Mankar, Smita LU ; Valsange, Nitin LU ; Sayed Ali Sayed, Mahmoud LU ; Pyo, Sang-Hyun LU ; Rehnberg, Nicola LU ; Lundmark, Stefan ; Hatti-Kaul, Rajni LU and Jannasch, Patric LU , et al. (2019) In Green Chemistry 21(24). p.6667-6684
Abstract
There is currently an intensive development of sugar-based building blocks toward the production of renewable high performance plastics. In this context, we report on the synthesis of a rigid diol with a spirocyclic structure via a one-step acid-catalyzed acetalation of fructose-sourced 5-hydroxymethylfurfural and pentaerythritol. Preliminary life cycle assessment (LCA) indicated that the spiro-diol produced 46% less CO2 emission than bio-based 1,3-propanediol. Polymerizations of the spiro-diol together with another sugar-based flexible 1,6-hexanediol for the production of polyesters and poly(urethane-urea)s were investigated, and reasonably high molecular weights were achieved when up to 20 or 60 mol% spiro-diol was used for polyesters or... (More)
There is currently an intensive development of sugar-based building blocks toward the production of renewable high performance plastics. In this context, we report on the synthesis of a rigid diol with a spirocyclic structure via a one-step acid-catalyzed acetalation of fructose-sourced 5-hydroxymethylfurfural and pentaerythritol. Preliminary life cycle assessment (LCA) indicated that the spiro-diol produced 46% less CO2 emission than bio-based 1,3-propanediol. Polymerizations of the spiro-diol together with another sugar-based flexible 1,6-hexanediol for the production of polyesters and poly(urethane-urea)s were investigated, and reasonably high molecular weights were achieved when up to 20 or 60 mol% spiro-diol was used for polyesters or poly(urethane-urea)s, respectively. The glass transition temperatures (Tg) of the polyesters and poly(urethane-urea)s significantly increased upon the incorporation of the rigid spirocyclic structure. On the other hand, it was observed that the spiro-diol was heat-sensitive, which could cause coloration andpartial crosslinking when >10%(with respect to dicarboxylate) was used for the polyester synthesis at high temperatures.The results indicated that the polymerization conditions have to be carefully controlled in order to avoid coloration and side reactions during the polyester formation when >10% of the spiro-diol is used. However, when the spiro-diol was used for the synthesis of polyurethanes at lower temperature, the side reactions were insignificant. This suggests that the new spiro-diol can be potentially suitable toward the production of sustainable rigid polyurethane materials like coatings or foams, as well as renewable polyesters after further optimization of the polymerization conditions. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Green Chemistry
volume
21
issue
24
pages
6667 - 6684
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85076711997
ISSN
1463-9270
DOI
10.1039/C9GC03055G
language
English
LU publication?
yes
additional info
The article was received on 30 Aug 2019, accepted on 10 Nov 2019 and first published on 13 Nov 2019
id
979ba73c-5276-4699-bbe3-f352f05faa7f
date added to LUP
2019-11-07 19:31:55
date last changed
2020-10-07 06:46:23
@article{979ba73c-5276-4699-bbe3-f352f05faa7f,
  abstract     = {There is currently an intensive development of sugar-based building blocks toward the production of renewable high performance plastics. In this context, we report on the synthesis of a rigid diol with a spirocyclic structure via a one-step acid-catalyzed acetalation of fructose-sourced 5-hydroxymethylfurfural and pentaerythritol. Preliminary life cycle assessment (LCA) indicated that the spiro-diol produced 46% less CO2 emission than bio-based 1,3-propanediol. Polymerizations of the spiro-diol together with another sugar-based flexible 1,6-hexanediol for the production of polyesters and poly(urethane-urea)s were investigated, and reasonably high molecular weights were achieved when up to 20 or 60 mol% spiro-diol was used for polyesters or poly(urethane-urea)s, respectively. The glass transition temperatures (Tg) of the polyesters and poly(urethane-urea)s significantly increased upon the incorporation of the rigid spirocyclic structure. On the other hand, it was observed that the spiro-diol was heat-sensitive, which could cause coloration andpartial crosslinking when >10%(with respect to dicarboxylate) was used for the polyester synthesis at high temperatures.The results indicated that the polymerization conditions have to be carefully controlled in order to avoid coloration and side reactions during the polyester formation when >10% of the spiro-diol is used. However, when the spiro-diol was used for the synthesis of polyurethanes at lower temperature, the side reactions were insignificant. This suggests that the new spiro-diol can be potentially suitable toward the production of sustainable rigid polyurethane materials like coatings or foams, as well as renewable polyesters after further optimization of the polymerization conditions.},
  author       = {Warlin, Niklas and Garcia Gonzalez, Nelly and Mankar, Smita and Valsange, Nitin and Sayed Ali Sayed, Mahmoud and Pyo, Sang-Hyun and Rehnberg, Nicola and Lundmark, Stefan and Hatti-Kaul, Rajni and Jannasch, Patric and Zhang, Baozhong},
  issn         = {1463-9270},
  language     = {eng},
  number       = {24},
  pages        = {6667--6684},
  publisher    = {Royal Society of Chemistry},
  series       = {Green Chemistry},
  title        = {A rigid spirocyclic diol from fructose-based 5-hydroxymethylfurfural: synthesis, life-cycle assessment, and polymerization for renewable polyesters and poly(urethane-urea)s},
  url          = {http://dx.doi.org/10.1039/C9GC03055G},
  doi          = {10.1039/C9GC03055G},
  volume       = {21},
  year         = {2019},
}