the copolymerization reactivity of diols with 2,5 ... · 11 esi-ms: q-tof premier ms (waters...

1

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: [email protected]

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: [email protected]

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.


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


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.


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)


y=0.09225x+0.5482 (R2=0.9959)

PEF/PBF-1/4


)/C (●) of PEF/PBF-1/4 versus concentration.


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)


y=0.03977x+0.8127 (R2=0.9940)

PEF/PBF-1/1



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)


y=-0.02699x+0.4699 (R2=0.9978)

PEF/PBF-2/1




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)


y=0.07672x+0.4984 (R2=0.9990)

PEF/PBF-3/1



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)


PEF/PBF-4/1




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)


PEF


)/C (●) of PEF versus concentration.


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.


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


11

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


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


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


14

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.


15

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).


16

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).


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


-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).


18

-50 0 50 100 150 200 250-15

-10

-5

0

5

10

Heat

flow

(mW

)

Temperature (oC)

Endo.


was heated and cooled at a rate of 40 o


-50 0 50 100 150 200 250-8

-6

-4

-2

0

2

4

6

8

Heat

flow

(mW

)

Temperature(oC)

Endo.




19

-50 0 50 100 150 200 250

-8

-6

-4

-2

0

2

4

6

8

Heat

flow

(mW

)

Temperature (oC)

Endo.


was heated and cooled at a rate of 40 o


-50 0 50 100 150 200 250

-8

-6

-4

-2

0

2

4

6

8

10

Heat

flow

(mW

)

Temperature (oC)

Endo.




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


-50 0 50 100 150 200 250

-2

-1

0

1

2

3

4

Heat

flow

(mW

)

Temperature (oC)

Endo.




the copolymerization reactivity of diols with 2,5 ... · 11 esi-ms: q-tof premier ms (waters...

Documents