Page 7 of 8
PleaseGdr oe en no Ct ha de jmu si st t mr yargins
DOI: 10.1039/C7GC03597G
Green Chemistry
catalysts were similar. These results indicate that
deposition of carbonaceous species on the Cu(50)-SiO
Notes and references
2
1
2
3
J.N. Chheda, G.W. Huber and J.A. Dumesic, Angew. Chem.
Int. Ed., 2007, 46, 7164-7183.
G. W. Huber, S. Iborra and A. Corma, Chem. Rev., 2006,
106, 4044-4098.
F. M. A. Geilen, B. Engendahl, A. Harwardt, W.
Marquardt, J. Klankermayer, and W. Leitner, Angew.
Chem. Int. Ed. 2010, 49, 5510-5514.
surface was negligible, owing to the selective
hydrogenation of HMF to yield DHMF.
Despite the high DHMF yield obtained in BuOH,
recovery of the product from this solvent by crystallization
following filtration was problematic because of its high
solubility in BuOH. Recovery of DHMF by distillation was
also challenging due to its high boiling point of 275 °C and
4
5
6
7
8
9
1
J.C. Serrano-Ruiz and J.A. Dumesic, Energy Environ. Sci.,
2011,
S. P. Teong, G. Yi and Y. Zhang, Green Chem.
015-2026.
H. A. Rass, N. Essayem, and M. Besson, ChemSusChem
015, , 1206-1217.
4, 83-99.
2
8
its low chemical stability. In addition, DHMF can be easily
degraded by condensation to yield humin during recovery
, 2014,16,
2
2
9
at room temperature.
2
8
As an alternative, we synthesized a DHMF-based
polymer, as this polymer can be easily separated from
BuOH by simple filtration (Fig. 6A). More specifically, the
prepared DHMF (~5.1 g) dissolved in BuOH was
polymerized by reaction with an equimolar amount of
succinic acid (4.7 g) to yield PFS.
N. K. Gupta, S. Nishimura, A. Takagaki and K. Ebitani
Green Chem., 2011, 13, 824-827.
P.P. Upare, D.W. Hwang, Y.K. Hwang, U.H. Lee, D.-Y. Hong
and J.-S. Chang, Green Chem., 2015, 17, 3310-3313.
Y. Román-Leshkov, C. J. Barrett, Z. Y. Liu and J. A.
Dumesic, Nature, 2007, 447, 982-985.
0 G.-H. Wang, J. Hilgert, F.H. Richter, F. Wang, H.-J.
Bongard, B. Spliethoff, C. Weidenthaler and F. Schüth,
Nat. Mater, 2014, 13, 293-300.
,
After allowing polymerization to proceed at 20 °C for
24 h, a conversion of 100% was achieved to give the solid
1
1
1 C. Zeng, H. Seino, J. Ren, K. Hatanaka and N. Yoshie,
Polymer, 2013, 54, 5351-5357.
2 C. Zeng, H. Seino, J. Ren, K. Hatanaka and N. Yoshie,
Macromolecules, 2013, 46, 1794-1802.
polymer product (~6.1 g), which was subsequently purified
1
by washing with diethyl ether. As indicated in Fig. 6B, the H
NMR spectrum of the recovered polymer exhibited all
characteristic peaks of PFS (i.e., methylene protons from
the succinate moiety at 2.68 ppm, methylene protons
linked to the furan ring at 5.05 ppm, and furanic protons at
13 J. Ohyama, A. Esaki, Y. Yamamoto, S. Arai and A. Satsuma,
RSC Advances, 2013, , 1033-1036.
4 M. Chatterjee, T. Ishizaka and H. Kawanami, Green Chem.,
014, 16, 4734-4739.
3
1
1
2
m
6.36 ppm). Furthermore, DSC analysis gave a T (melting
5 M. Tamura, K. Tokonami, Y. Nakagawa and K. Tomishige,
Chem. Commun., 2013, 49, 7034-7036.
onset temperature) of 99 °C, which is between those of
DHMF (73 °C) and succinic acid (189 °C) (Fig. S3). Finally,
GPC analysis confirmed that the molecular weight (Mw) of
the obtained polymer was ~4046 (Fig. S4) and TGA
confirmed that it was stable below 250 °C (Fig. S5). We
therefore conclude that PFS was successfully produced
from fructose in the presence of succinic acid.
16 R. Alamillo, M. Tucker, M. Chia, Y. Pagán-Torres and J.
Dumesic, Green Chem., 2012, 14, 1413-1419.
1
7 X. Kong, R. Zheng, Y. Zhu, G. Ding, Y. Zhu and Y.-W. Li,
Green Chem., 2015, 17, 2504-2514.
8 X. Kong, Y. Zhu, H. Zheng, F. Dong, Y. Zhu and Y.-W. Li,
1
RSC Advances, 2014,
19 Y. Zhu, X. Kong, H. Zheng, G. Ding, Y. Zhu and Y.-W. Li,
Catal. Sci. Technol. 2015, , 4208-4217.
0 A.J. Kumalaputri, G. Bottari, P.M. Erne, H.J. Heeres and K.
Barta, ChemSusChem, 2014, , 2266-2275.
4, 60467-60472.
5
2
2
7
4
. Conclusions
1 G. Tsilomelekis, M. J. Orella, Z. Lin, Z. Cheng, W. Zheng, V.
Nikolakis and D. G. Vlachos, Green Chem., 2016, 18,1983 -
An integrated process for the production of DHMF from fructose
was developed through a combination of dehydration over
1
993.
2 X. Xiang, J. Cui, G. Ding, H. Zheng, Y. Zhu, and Y.-W. Li, ACS
Sustainable Chem. Eng. 2016, , 4506−4510.
2
2
Amberlyst-15 and subsequent hydrogenation over a Cu(50)-SiO
2
4
nanocomposite, using BuOH as the reaction solvent. The as-
synthesized DHMF was then successfully transformed into its
polymer, PFS, by reaction with succinic acid. On this basis, we
conclude that the present protocol is a novel and effective
method to produce a biomass-derived polymer from fructose in
both an environmental and an industrial context.
3 C. M. Lew, N. Rajabbeigi, and M. Tsapatsis, Ind. Eng.
Chem. Res. 2012, 51, 5364−5366.
24 P.P. Upare, Y.K. Hwang, J.-M. Lee, D.W. Hwang and J.-S.
Chang, ChemSusChem, 2015, , 2345-2357.
2
8
5 M. Lee, Y.K. Hwang, J.-S. Chang, H.-J. Chae, D.W. Hwang,
Catal. Comm. 2016, 84, 5-10.
6 P.P. Upare, M.-G. Jeong, Y.K. Hwang, D.H. Kim, Y.D. Kim,
D.W. Hwang, U.H. Lee and J.-S. Chang, App. Catal. A:
Gen., 2015, 491, 127-135.
2
Acknowledgements
27 D.W. Hwang, P. Kashinathan, J.M. Lee, J.H. Lee, U.h. Lee,
J.-S. Hwang, Y.K. Hwang and J.-S. Chang, Green Chem.,
This work was supported by the R&D Program of the
Institutional Research Program of KRICT [KK-1701-C0] and
the Korea Research Fellowship Program funded by the
2
011, 13, 1672-1675.
2
2
8 http://www.chemicalbook.com/ChemicalProductPropert
y_EN_CB4417778.htm
9 A. B. Jain and P. D. Vaidya, Int. J. Chem. Kinetics, 2016,
National
Research
Foundation
of
Korea
48, 318-328.
[2017H1D3A1A02053077].
This journal is © The Royal Society of Chemistry 2017
Green Chem. 2017, 00, 1-3 | 7
Please do not adjust margins