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ELECTRONIC SUPPLEMENTARY INFORMATION Sustainable Aromatic Copolyesters via Ring Opening Polymerization: Poly(butylene 2,5-furandicarboxylate-co-terephthalate)s Juan Carlos Morales-Huerta, Antxon Martínez de Ilarduya, Sebastián Muñoz-Guerra* Department d’Enginyeria Química, Universitat Politècnica de Catalunya, ETSEIB, Diagonal 647, 08028 Barcelona, Spain
Contents: 6 pages, 6 figures
1
ELECTRONIC SUPPLEMENTARY INFORMATION Sustainable Aromatic Copolyesters via Ring Opening Polymerization: Poly(butylene 2,5-furandicarboxylate-co-terephthalate)s Juan Carlos Morales-Huerta, Antxon Martínez de Ilarduya, Sebastián Muñoz-Guerra* Department d’Enginyeria Química, Universitat Politècnica de Catalunya, ETSEIB, Diagonal 647, 08028 Barcelona, Spain
d
O b C d c O e
a
a
O C O n
O C O
O C O 166.0 165.8 165.6 165.4 165.2 165.0 (ppm)
c
e
CDCl3
d
b TMS
200 180 160 140 120 100
80
60
40
20
0
(ppm)
a
TMS
CDCl3
d
8
7
6
5
e
4
3
2
1
0
(ppm)
Figure S1.13C (top) and 1H (bottom) NMR of c(BT)n.
2
a O e
d O
C c
b O
C
O O
O C O
O
O
C
d n
a
e
O
CDCl3
c b TMS
200 180 160 140 120 100
80
60
40
20
0
(ppm)
TMS
a d
e
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
(ppm)
Figure S2.13C (top) and 1H (bottom) NMR of c(BF)n.
3
c(BT)2
c(BT)3
c(BT)4
CHCl3 0
5
10
15
20
25
30
35
40
time (min)
c(BF)2
c(BF)3
c(BF)4 CHCl3 0
5
10
15
20
25
30
35
40
45
time (min)
Figure S3. HPLC of c(BT)n (top) and c(BF)n (bottom).
c(BF)2
c(BF)3 c(BF)4
CHCl3
Linear Oligomers
DCM
c(BF)3 c(BF)4 Linear Oligomers
c(BF)2
THF
CHCl3 0
5
10
15
20 25 time (min)
30
35
40
Figure S4. Compared HPLC of the crude product of the HD ciclyzation reaction of BDO and FDCA-Cl2 carried out in DCM (top) and THF (bottom).
4
a
e O
d
O
bO
a a'
c
c'
PBF
O c
d'
O
O
e' O
O a' C b' c' C O y
x
TFA
CDCl3
e e'
d d'
co PBF90T10 co PBF80T20 co PBF60T40 co PBF50T50 co PBF40T60 co PBF20T80 co PBF10T90 PBT 180
160
140
120
100 80 (ppm)
60
40
20
0
a a'
PBF
TMS
e e'
d d'
CDCl3
co PBF90T10 co PBF80T20 co PBF60T40 co PBF50T50 co PBF40T60 co PBF20T80 co PBF10T90 PBT 9
8
7
6
5
4
(ppm)
3
2
1
0
Figure S5. 13C (top) and 13H (bottom) NMR spectra of coPBFxTy.
5
2
ln(-ln(1-Xt))
0
-2 PBF (146 °C) coPBF20T80 (175 °C)
-4
coPBF10 T90 (186 °C) PBT (204 °C)
-6 -1
0
1
2
3
ln(t-t0)
Figure S6. Double logarithmic plots of crystallinity versus time for the isothermal crystallization of PBT, PBF, coPBF10T90 and coPBF20T80.
6
Contents: 6 pages, 6 figures
1
ELECTRONIC SUPPLEMENTARY INFORMATION Sustainable Aromatic Copolyesters via Ring Opening Polymerization: Poly(butylene 2,5-furandicarboxylate-co-terephthalate)s Juan Carlos Morales-Huerta, Antxon Martínez de Ilarduya, Sebastián Muñoz-Guerra* Department d’Enginyeria Química, Universitat Politècnica de Catalunya, ETSEIB, Diagonal 647, 08028 Barcelona, Spain
d
O b C d c O e
a
a
O C O n
O C O
O C O 166.0 165.8 165.6 165.4 165.2 165.0 (ppm)
c
e
CDCl3
d
b TMS
200 180 160 140 120 100
80
60
40
20
0
(ppm)
a
TMS
CDCl3
d
8
7
6
5
e
4
3
2
1
0
(ppm)
Figure S1.13C (top) and 1H (bottom) NMR of c(BT)n.
2
a O e
d O
C c
b O
C
O O
O C O
O
O
C
d n
a
e
O
CDCl3
c b TMS
200 180 160 140 120 100
80
60
40
20
0
(ppm)
TMS
a d
e
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
(ppm)
Figure S2.13C (top) and 1H (bottom) NMR of c(BF)n.
3
c(BT)2
c(BT)3
c(BT)4
CHCl3 0
5
10
15
20
25
30
35
40
time (min)
c(BF)2
c(BF)3
c(BF)4 CHCl3 0
5
10
15
20
25
30
35
40
45
time (min)
Figure S3. HPLC of c(BT)n (top) and c(BF)n (bottom).
c(BF)2
c(BF)3 c(BF)4
CHCl3
Linear Oligomers
DCM
c(BF)3 c(BF)4 Linear Oligomers
c(BF)2
THF
CHCl3 0
5
10
15
20 25 time (min)
30
35
40
Figure S4. Compared HPLC of the crude product of the HD ciclyzation reaction of BDO and FDCA-Cl2 carried out in DCM (top) and THF (bottom).
4
a
e O
d
O
bO
a a'
c
c'
PBF
O c
d'
O
O
e' O
O a' C b' c' C O y
x
TFA
CDCl3
e e'
d d'
co PBF90T10 co PBF80T20 co PBF60T40 co PBF50T50 co PBF40T60 co PBF20T80 co PBF10T90 PBT 180
160
140
120
100 80 (ppm)
60
40
20
0
a a'
PBF
TMS
e e'
d d'
CDCl3
co PBF90T10 co PBF80T20 co PBF60T40 co PBF50T50 co PBF40T60 co PBF20T80 co PBF10T90 PBT 9
8
7
6
5
4
(ppm)
3
2
1
0
Figure S5. 13C (top) and 13H (bottom) NMR spectra of coPBFxTy.
5
2
ln(-ln(1-Xt))
0
-2 PBF (146 °C) coPBF20T80 (175 °C)
-4
coPBF10 T90 (186 °C) PBT (204 °C)
-6 -1
0
1
2
3
ln(t-t0)
Figure S6. Double logarithmic plots of crystallinity versus time for the isothermal crystallization of PBT, PBF, coPBF10T90 and coPBF20T80.
6
