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Supporting information for
The copolymerization reactivity of diols with 2,5-
furandicarboxylic acid for furan-based copolyester materials
Jiping Ma,abc Yi Pang,*a Min Wang,bc Jie Xu,*b Hong Ma,b and Xin Nieb
a
E-mail: yp5@uakron.edu
Department of Chemistry, The University of Akron, Akron, OH, 44325, USA
b Dalian National Lab for Clean Energy, State Key Laboratory of Catalysis, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, P. R. China
Fax: (+86)-411-84379245; E-mail: xujie@dicp.ac.cn
c
Table of Contents:
Graduate University of the Chinese Academy of Sciences, Beijing 100039, P. R. China
1. Synthesis of 2,5-furandicarboxylic acid (FDCA) (pp.2-4).
2. Intrinsic viscosity determination (pp.5-8).
3. Reactivity of diols reaction with FDCA determination (pp.9-14).
4. Thermal properties determination (pp.15-20).
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
2
1. Synthesis of 2,5-furandicarboxylic acid (FDCA).
Chemicals
NaOH was purchased from Aldrich. KMnO4
Procedure
was from Acros Organics. HCl (37%) was
purchased from Mallinckrodt Baker, Inc. All reagents were of analytical grade unless otherwise
mentioned and used as received.
DFF (1.99 g, 16.07 mmol) and 50 mL H2O was placed in a 250 mL round-bottom flask
equipped with a magnetic stirrer. A solution of KMnO4 (3.90 g, 24.65 mmol) in 50 mL of 10%
aq. NaOH was added dropwise with stirring over a period of 0.5 h. Then, the mixture was
allowed to stir for an additional 1 h at room temperature, and the resulting precipitate was
removed by filtration. The filtrate was treated with a 37% HCl solution until PH = 1 or less. A
pale yellow solid (1.95 g, 78%) was isolated by suction filtration, washed with water, and
dried. 1H NMR (300 MHz, DMSO-d6, 298K): 13.63 (2H, s, -COOH), 7.29 (2H, s, furan-H); 13C
NMR: 158.92 (-COOH), 147.07 (C2/C5), 118.40 (C3/C4). FT-IR (KBr, νmax/cm-1
): 3152 and
3126 (C-H); 1693 (C=O); 1573 (C=C); 1423 and 1275 (furan C-O-C); 1040, ring breathing; 961,
851, and 763 bending motions associated with the 2,5-disubstituted furan ring.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
3
Figure S1. 1H NMR (DMSO-d6
) of 2,5-furandicarboxylic acid.
Figure S2. 13C NMR (DMSO-d6
) of 2,5-furandicarboxylic acid.
OOO
OHHO
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
4
4000 3500 3000 2500 2000 1500 1000 500-10
0
10
20
30
40
50
Tran
smitt
ance
(%)
Wavenumber (cm-1)
Figure S3. FT-IR (KBr) of 2,5-furandicarboxylic acid.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
5
2. Intrinsic viscosity determination
0.15 0.20 0.25 0.30 0.350.44
0.45
0.46
0.47
0.48
y=-0.01734x+0.4520 (R2=0.9988)
y=0.08765x+0.4517 (R2=0.9996)
(Inη r) /
C or
ηsp
/C (d
l/g)
Concentration (g/dl)
PBF
Figure S4. ηsp/C (■) or (Inηr
)/C (●) of PBF versus concentration.
0.24 0.32 0.40 0.48
0.52
0.54
0.56
0.58
y=-0.05455x+0.5476 (R2=0.9934)
(Inη r)/
C or
ηsp
/C (d
l/g)
Concentration (g/dl)
y=0.09225x+0.5482 (R2=0.9959)
PEF/PBF-1/4
Figure S5. ηsp/C (■) or (Inηr
)/C (●) of PEF/PBF-1/4 versus concentration.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
6
0.10 0.15 0.20 0.25 0.30 0.350.72
0.74
0.76
0.78
0.80
0.82
0.84
y=-0.2303x+0.8063 (R2=0.9990)
(Inη r) /
C or
ηsp
/ C(d
l/g)
Concentration (g/dl)
y=0.03977x+0.8127 (R2=0.9940)
PEF/PBF-1/1
Figure S6. ηsp/C (■) or (Inηr
)/C (●) of PEF/PBF-1/1 versus concentration.
0.15 0.20 0.25 0.30 0.350.45
0.46
0.47
0.48
0.49
0.50
y=0.08531x+0.4698 (R2=0.9988)
(Inη r)/
C or
ηsp
/C (d
l/g)
Concentration (g/dl)
y=-0.02699x+0.4699 (R2=0.9978)
PEF/PBF-2/1
Figure S7. ηsp/C (■) or (Inηr
)/C (●) of PEF/PBF-2/1 versus concentration.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
7
0.12 0.16 0.20 0.24 0.28 0.32
0.49
0.50
0.51
0.52
y=-0.04448x+0.4978 (R2=0.9975)
(Inη r)/
C or
ηsp
/C (d
l/g)
Concentration (g/dl)
y=0.07672x+0.4984 (R2=0.9990)
PEF/PBF-3/1
Figure S8. ηsp/C (■) or (Inηr
)/C (●) of PEF/PBF-3/1 versus concentration.
0.10 0.15 0.20 0.25 0.30 0.350.48
0.49
0.50
0.51
0.52
y=-0.05804x+0.4998 (R2=0.9989)
y=0.06258x+0.5003 (R2=0.9939)
(Inη r)/
C or
ηsp
/C (d
l/g)
Concentration (g/dl)
PEF/PBF-4/1
Figure S9. ηsp/C (■) or (Inηr
)/C (●) of PEF/PBF-4/1 versus concentration.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
8
0.15 0.20 0.25 0.30 0.350.44
0.45
0.46
0.47
0.48
y=-0.05728x+0.4646 (R2=0.9938)
y=0.04521x+0.4654 (R2=0.9977)
(Inη r)/
C or
ηsp
/C (d
l/g)
Concentration (g/dl)
PEF
Figure S10. ηsp/C (■) or (Inηr
)/C (●) of PEF versus concentration.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
9
3. Reactivity of diols reaction with FDCA determination
0.00 0.05 0.10 0.15 0.20 0.25
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Ai
/As
Ci/Cs
y=14.1197x+0.06263 (R2=0.9999)
Figure S11. Standard line of FDCA using malonic acid as internal standard.
0 50 100 150 200 250 3000
20
40
60
80
100
react with EG react with BG
FDCA
Con
vers
ion
(%)
time (min)
Figure S12. Plot of FDCA conversion as a function of reaction time.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
10
Figure S13. Changes of HPLC spectra of FDCA reaction with EG as a function of reaction time
(The first samples were taken after 15 min, and then at 15-min intervals for 60 min, and then at
1-h intervals for 5 h).
0 50 100 150 200 250 300
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
FDCA 3a 4a
Ai/A
s
time(min)
Figure S14. Plot of area ratio of FDCA, 3a and 4a to that of internal standard as a function of
reaction time.
AU
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
分钟
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
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ESI-MS: Q-TOF Premier MS (Waters Corporation) using the ESI emitters. The MS was
operated in positive V-mode with typical resolving power of at least 8000. The MS detector was
calibrated from m/z 50 to 1000 by the MS/MS fragment ions of GFP. The radio frequency (RF)
offset applied to the quadrupole mass analyzer was adjusted in order that the LC/MS data were
effectively acquired from m/z 50 to 1000. The spectrum integration time was 0.9 s for MS scan
(m/z 50–1000) and 1.2 s for MS/MS scan (m/z 50–1000) with an inter-scan delay time of 0.05 s.
Figure S15. ESI-MS spectrum of 3a.
m/z10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
%
0
100ZHAOL-MS2_201 12 (0.212) Cm (3:20) TOF MSMS 201.03ES+
1.33e4139.0056
98.9883
157.0142
140.0075
183.0279
158.0189
159.0175
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
12
Figure S16. ESI-MS spectrum of 4a.
Figure S17. Changes of HPLC spectra of FDCA reaction with BG as a function of reaction time
(The first samples were taken after 15 min, and then at 15-min intervals for 60 min).
AU
0.000
0.010
0.020
0.030
0.040
0.050
0.060
0.070
0.080
0.090
0.100
0.110
0.120
0.130
分钟
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
13
10 20 30 40 50 600.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
FDCA 3b 4b
Ai/A
s
time (min)
Figure S18. Plot of area ratio of FDCA, 3b and 4b to that of internal standard as a function of
reaction time.
Figure S19. ESI-MS spectrum of 3b.
m/z50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
%
0
100QHQ_20110228_SAMPLE_229 9 (0.159) Cm (2:16) TOF MSMS 229.09ES+
2.37e373.1012
229.0916
157.0359
136.9672189.0630
233.0490
235.0827
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
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Figure S20. ESI-MS spectrum of 4b.
0 20 40 60 80 100 120
-4
-3
-2
-1
0
In(C
t/C0)
t(min)
Figure S21. Relationship of In(Ct/C0) and reaction time t of FDCA reacting with 1,3-
trimethylene glycol (■) and 1,5-pentylene glycol (▲), respectively. Ct and C0
m/z50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
%
0
100QHQ_20110228_SAMPLE_301 39 (0.689) Cm (4:40) TOF MSMS 301.14ES+
6.19e3229.0916
73.1012
302.3243301.1506
230.0931
283.1392
303.3275
307.1448
represent the
concentration of FDCA at time t and at the beginning of the reaction, respectively.
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
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4. Thermal properties determination
0 100 200 300 400 500 6000
20
40
60
80
100 PBF PEF/PBF-1/4 PEF/PBF-1/1 PEF/PBF-2/1 PEF/PBF-3/1 PEF/PBF-4/1 PEF
Wei
ght l
oss
(%)
Temperature (oC)
Figure S22. Thermogravimetric curves of as-prepared copolyesters. Conditions: sample was
heated at a rate of 10 °C/min under nitrogen flow (25 mL/min).
50 100 150 200
PEF
PEF/PBF-4/1
PEF/PBF-3/1
PEF/PBF-2/1
PEF/PBF-1/1
PEF/PBF-1/4
Temperature (oC)
PBF
Endo.
Figure S23. The first DSC heating traces of the as-prepared copolyesters. Conditions: the sample
was heated at a rate of 40 oC/min under nitrogen flow (25 mL/min).
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0 50 100 150 200
PEFPEF/PBF-4/1
PEF/PBF-3/1
PEF/PBF-2/1
PEF/PBF-1/1
PEF/PBF-1/4
Temperature (oC)
PBF
Endo.
Figure S24. The second DSC heating traces of the as-prepared copolyesters. Conditions: the
sample was heated at a rate of 40 o
C/min under nitrogen flow (25 mL/min).
-50 0 50 100 150 200 250
-4
-2
0
2
4
6
Hea
t flo
w (m
W)
Temperature (oC)
Endo.
Figure S25. DSC traces of the as-prepared polyester PBF. Conditions: the sample was heated
and cooled at a rate of 10 oC/min under nitrogen flow (25 mL/min).
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
17
-50 0 50 100 150 200 250
-8-6-4-2024
68
1012
Heat
flow
(mW
)
Temperature (oC)
Endo.
Figure S26. DSC traces of the as-prepared polyester PBF. Conditions: the sample was heated
and cooled at a rate of 40 o
C/min under nitrogen flow (25 mL/min).
-50 0 50 100 150 200 250-4
-2
0
2
4
6
8
Heat
flow
(mW
)
Temperature (oC)
Endo.
Figure S27. DSC traces of the as-prepared copolyester PEF/PBF-1/4. Conditions: the sample
was heated and cooled at a rate of 40 oC/min under nitrogen flow (25 mL/min).
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
18
-50 0 50 100 150 200 250-15
-10
-5
0
5
10
Heat
flow
(mW
)
Temperature (oC)
Endo.
Figure S28. DSC traces of the as-prepared copolyester PEF/PBF-1/1. Conditions: the sample
was heated and cooled at a rate of 40 o
C/min under nitrogen flow (25 mL/min).
-50 0 50 100 150 200 250-8
-6
-4
-2
0
2
4
6
8
Heat
flow
(mW
)
Temperature(oC)
Endo.
Figure S29. DSC traces of the as-prepared copolyester PEF/PBF-2/1. Conditions: the sample
was heated and cooled at a rate of 40 oC/min under nitrogen flow (25 mL/min).
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
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-50 0 50 100 150 200 250
-8
-6
-4
-2
0
2
4
6
8
Heat
flow
(mW
)
Temperature (oC)
Endo.
Figure S30. DSC traces of the as-prepared copolyester PEF/PBF-3/1. Conditions: the sample
was heated and cooled at a rate of 40 o
C/min under nitrogen flow (25 mL/min).
-50 0 50 100 150 200 250
-8
-6
-4
-2
0
2
4
6
8
10
Heat
flow
(mW
)
Temperature (oC)
Endo.
Figure S31. DSC traces of the as-prepared copolyester PEF/PBF-4/1. Conditions: the sample
was heated and cooled at a rate of 40 oC/min under nitrogen flow (25 mL/min).
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
20
-50 0 50 100 150 200 250
-6
-4
-2
0
2
4
6
8
Heat
flow
(mW
)
Temperature (oC)
Endo.
Figure S32. DSC traces of the as-prepared polyester PEF. Conditions: the sample was heated
and cooled at a rate of 40 o
C/min under nitrogen flow (25 mL/min).
-50 0 50 100 150 200 250
-2
-1
0
1
2
3
4
Heat
flow
(mW
)
Temperature (oC)
Endo.
Figure S33. DSC traces of the as-prepared copolyester PEF/PBF-1/1. Conditions: the sample
was heated and cooled at a rate of 10 oC/min under nitrogen flow (25 mL/min).
Electronic Supplementary Material (ESI) for Journal of Materials ChemistryThis journal is © The Royal Society of Chemistry 2012
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