advances in the synthesis of bio-based aromatic polyesters: novel copolymers derived ... · 2016....
TRANSCRIPT
Advances in the synthesis of bio-based aromatic polyesters: novel
copolymers derived from vanillic acid and -caprolactone
Claudio Gioia, Maria Barbara Banella, Paola Marchese, Micaela Vannini, Martino Colonna,
Annamaria Celli*
Department of Civil, Chemistry, Environmental and Materials Engineering, University of Bologna,
Via Terracini 28, 40131 Bologna, Italy.
*Corresponding author. Tel: 0039-51-2090349; fax: 0039-51-2090322.
E-mail address: [email protected] (A. Celli)
Electronic Supporting information (ESI) Contents:
A) Figure S1: 1H-NMR spectrum of poly(caprolactone) (PCL)
B) Figure S2: 13C-NMR spectrum of poly(caprolactone) (PCL)
C) Figure S3: 1H-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-
co-CL)-20/80
D) Figure S4: 13C-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone)
P(EV-co-CL)-20/80
E) Figure S5: 1H-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-
co-CL)-50/50
F) Figure S6: 13C-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone)
P(EV-co-CL)-50/50
G) Figure S7: 1H-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-
co-CL)-80/20
H) Figure S8:13C-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-
co-CL)-80/20
I) Figure S9: 1H-NMR spectrum of poly(ethylene vanillate) PEV
J) Figure S10: 13C-NMR spectrum of poly(ethylene vanillate) PEV
K) Equation S1-S4: Quantitative determination of the molar fractions (F) of EV-EV, EV-CL, CL-CL
and CL-EV sequences by 1H-NMR signals
L) Equation S5-S8: Quantitative determination of the molar fractions (F) of EV-EV, EV-CL, CL-CL and
CL-EV sequences by 13C-NMR signals
M) Equation S9-S11: Quantitative determination of the average sequence lengths of EV-EV and CL-CL
dyads (LEV-EV and LCL-CL) and the randomness degree (B)
Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2016
Figure S1: 1H-NMR spectrum of poly(caprolactone) (PCL)
Figure S2: 13C-NMR spectrum of poly(caprolactone) (PCL)
1
0
0
0.0 0.0 0.5 0.5 1.0 1.0 1.5 1.5 2.0 2.0 2.5 2.5 3.0 3.0 3.5 3.5 4.0 4.0 4.5 4.5 5.0 5.0 5.5 5.5 6.0 6.0 6.5 6.5 7.0 7.0 7.5 7.5 8.0 8.0
CHCl3
ppm
TMS
g k h, j
i
180 180 200 200 20 20 40 40 60 60 80 80 100 110 120 120 140 140 160 160
CDCl3
ppm
g
k
h
i
j
CF3COOD
3
CF3COOD
O
k
j
i
hO
g3
n
Figure S3: 1H-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-co-CL)-
20/80
Figure S4: 13C-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-co-
CL)-20/80
0.0 0.0 0.5 0.5 1.0 1.0 1.5 1.5 2.0 2.0 2.5 2.5 3.0 3.0 3.5 3.5 4.0 4.0 4.5 4.5 5.0 5.0 5.5 5.5 6.0 6.0 6.5 6.5 7.0 7.0 7.5 7.5 8.0 8.0
CHCl3
ppm
TMS
g
k
h, j
i
e
d
f f ’
a
a’
b
b’, g’
c
i’ h’
25 25 50 50 75 75 100 100 125 125 150 150 175 175 200 200
CDCl3
g
k
h
i
j
CF3COOD
3
CF3COOD
a b 4 2
1
ppm
c e d
f 5 6 7
ppm 20 40 60 80 100 120 140 160 160 180 200
CDCl3
CF3COOD
CF3COOD
j g k h
i a
b
c
e d
f 5
4 3 1 2 6 7
Figure S5:1H-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-co-CL)-
50/50
Figure S6: 13C-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-co-
CL)-50/50
0.0 0.0 0.5 0.5 1.0 1.0 1.5 2.0 2.0 2.5 2.5 3.0 3.0 3.5 3.5 4.0 4.0 4.5 4.5 5.0 5.0 5.5 5.5 6.0 6.0 6.5 6.5 7.0 7.0 7.5 7.5 8.0 8.0
CHCl3
ppm
TMS
g
k
h, j
i
e
d
f f ’
a
b
a’ b’, g’
c
i’ h’
Figure S7: 1H-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-co-CL)-
80/20
Figure S8: 13C-NMR spectrum of copolymer poly(ethylene vanillate-co-caprolactone) P(EV-co-
CL)-80/20
h’ i’
0.0 0.0 0.5 0.5 1.0 1.0 1.5 1.5 2.0 2.0 2.5 2.5 3.0 3.0 3.5 3.5 4.0 4.0 4.5 4.5 5.0 5.0 5.5 5.5 6.0 6.0 6.5 6.5 7.0 7.0 7.5 7.5 8.0 8.0
CHCl3
ppm
TMS
g k
h, j
i
e
d
f
f ’
a
a’
b
b’, g’
c
25 25 50 50 75 75 100 100 125 125 150 150 175 175 200
CF3COOD
25 50 75 100 125 150 175 200
CDCl3 c
j g
k
h i
CF3COOD
a
b
ppm
e d
f
5
1
4 2
6
7
3
200
ppm
CDCl3
CF3COOD
CF3COOD
c
d
a
6
b e f 5
7
1
25 25 50 50 75 75 100 100 125 125 150 150 175 175 200 200
Figure S9: 1H-NMR spectrum of poly(ethylene vanillate) PEV
Figure S10: 13C-NMR spectrum of poly(ethylene vanillate) PEV
0.0 0.0 0.5 0.5 1.0 1.0 1.5 1.5 2.0 2.0 2.5 2.5 3.0 3.0 3.5 3.5 4.0 4.0 4.5 4.5 5.0 5.0 5.5 5.5 6.0 6.0 6.5 6.5 7.0 7.0 7.5 7.5 8.0 8.0
a b
c
e
d
f TMS
CHCl3
ppm
O
O
OO
d
e
f
b
a
c
15
6
7
Equation S1-S4: Quantitative determination of the molar fractions (F) of EV-EV, EV-CL, CL-CL and CL-
EV sequences by 1H-NMR signals
𝐹𝐸𝑉−𝐸𝑉 =𝐼𝑓
𝐼𝑓 + 𝐼𝑓′ 𝑆1
𝐹𝐸𝑉−𝐶𝐿 =𝐼𝑓′
𝐼𝑓 + 𝐼𝑓′ 𝑆2
𝐹𝐶𝐿−𝐶𝐿 =𝐼𝑖
𝐼𝑖 + 𝐼𝑖′ 𝑆3
𝐹𝐶𝐿−𝐸𝑉 =𝐼𝑖′
𝐼𝑖 + 𝐼𝑖′ 𝑆4
Equation S5-S8: Quantitative determination of the molar fractions (F) of EV-EV, EV-CL, CL-CL and CL-EV
sequences by 13C-NMR signals
𝐹𝐸𝑉−𝐸𝑉 =𝐼1
𝐼1 + 𝐼2 𝑆5
𝐹𝐸𝑉−𝐶𝐿 =𝐼2
𝐼1 + 𝐼2 𝑆6
𝐹𝐶𝐿−𝐶𝐿 =𝐼3
𝐼3+𝐼4 𝑆7
𝐹𝐶𝐿−𝐸𝑉 =𝐼4
𝐼3 + 𝐼4 𝑆8
Equation S9-S11: Quantitative determination of the average sequence lengths of EV-EV and CL-CL dyads
(LEV-EV and LCL-CL) and the randomness degree (B)
𝐿𝐸𝑉−𝐸𝑉 =𝐹𝐸𝑉−𝐸𝑉
𝐹𝐸𝑉−𝐶𝐿+ 1 𝑆9
𝐿𝐶𝐿−𝐶𝐿 =𝐹𝐶𝐿−𝐶𝐿
𝐹𝐶𝐿−𝐸𝑉+ 1 𝑆10
𝐵 =1
𝐿𝐸𝑉−𝐸𝑉+
1
𝐿𝐶𝐿−𝐶𝐿 𝑆11
