Electronic Supplementary Information
Synthesis, Characterization and Evaluation of Novel Polyhydantoins as Gas Separation Membranes
Rubén Tejero, Ángel E. Lozano, Cristina Álvarez, Javier de Abajo
FIGURE S1 1H and 13C NMR Spectra in CDCl3 of Bisiminoacetate BIS-1 .
FIGURE S2 1H and 13C NMR Spectra in CDCl3 of Bisiminoacetate BIS-2.
FIGURE S3 1H and 13C NMR Spectra in CDCl3 of Diisocyanate DII-1.
FIGURE S4 1H and 13C NMR Spectra in CDCl3 of Diisocyanates DII-2.
TABLE S1 ATR-FTIR, 1H and 13C NMR in DMSO-d6 and Elemental Analysis of PHYs.
FIGURE S5 ATR-FTIR Spectra of PHYs.
FIGURE S6 1H and 13C NMR Spectra in DMSO-d6 of PHYs.
FIGURE S7 1H and 13C NMR Spectra in DMSO-d6 of PHYs.
FIGURE S8 1H and 13C NMR Spectra in DMSO-d6 of PHYs.
FIGURE S9 1H and 13C NMR Spectra in DMSO-d6 of PHYs.
1
c
a
b
CHCl
3
8
f
7
e d
6
5
4
3
2
1
0
 (ppm)
C4
C7
C2
C1
CHCl
3
C3
200
180
160
C8
140
C6
120
C5
100
80
60
40
20
 (ppm)
FIGURE S1 1H and 13C NMR Spectra in CDCl3 of Bisiminoacetate BIS-1.
2
0
a
b
d
c
e,f,g
h
10
9
8
7
6
5
4
3
2
1
0
 (ppm)
C6
C5
C10,C11,C12
C1
C13
C2
C14
C9 C7
CHCl
C4
200
180
160
140
120
100
 (ppm)
80
3
C3
C8
60
40
20
0
FIGURE S2 1H and 13C NMR Spectra in CDCl3 of Bisiminoacetates BIS-2.
3
b a
c,d,e
f
12
11
10
9
8
7
6
5
4
3
2
1
0
 (ppm)
C4 C3,C1
C9,C10
C12
C7 C2
CHCl
C11
C8
C6
C5
200
180
160
140
3
120
100
80
60
40
 (ppm)
FIGURE S3 1H and 13C NMR Spectra in CDCl3 of B Diisocyanates DII-1.
4
20
0
e
c
a b
10
9
8
7
d
6
5
4
3
2
1
0
 (ppm)
C13
C9
C6 C10
C3
C1
CHCl
C4,C5,C7, 3
C2
C12
C8 C11
200
180
160
140
120
100
80
60
40
20
0
 (ppm)
FIGURE S4 1H and 13C NMR Spectra in CDCl3 of Diisocyanates DII-2.
5
TABLE S1. ATR-FTIR, 1H and 13C NMR in DMSO-d6 and Elemental Analysis of PHYs.
Polymer
PHY-1
Frequency (cm-1)
1H, 13C
C-H Ar. (3043)
8.00 (s, 1H; Ar)
C-H Alif. (2900)
7.50-7.37 (m, 11H; Ar)
C=O (1777)
4.63 (s, 4H; CH2)
C=O (1714)
4.08 (s, 2H; CH2)
NMR in DMSO-d6
Elemental Analysis
C25H18N4O4
%C
%H
%N
Calcd.
68.49
4.14
12.78
Found
66.90
4.27
12.48
%C
%H
%N
168.0 (2C), 153.3 (2C), 140.9 (2C), 138.6 (2C), 129.9 (2C),
129.6, 129.1 (5C), 127.0 (4C), 113.8, 108.6, 50.0 (2C), 40.3
PHY-2
C-H Ar. (3039)
7.93 (d, J = 7.6 Hz, 2H; Ar)
C44H30N4O4
CH Alif. (2911)
7.64 (d, J = 7.6 Hz, 2H; Ar)
C=O (1778)
7.52-7.25 (m, 16H; Ar)
Calcd.
77.86
4.46
8.25
C=O (1717)
7.14 (d, J = 8.5 Hz, 4H; Ar)
Found
76.61
4.64
8.17
%C
%H
%N
4.55 (s, 4H; CH2)
4.03 (s, 2H; CH2)
168.1 (2C), 153.2 (2C), 150.4 (2C), 140.9 (2C), 140.8 (2C), 139.4
(2C), 136.6 (2C), 129.8 (2C), 129.1 (5C), 128.2 (3C), 127.9 (2C),
127.8 (2C), 126.9 (5C), 125.9 (2C), 120.6 (2C), 118.6 (3C), 63.9,
49.9 (2C), 40.3
PHY-3
C-H Ar. (3056)
7.95 (m, J = 8.4 Hz, 2H; Ar)
C28H18N2O2
C=O (1776)
7.55 (d, J = 7.8 Hz, 4H; Ar)
C=O (1718)
7.46-7.28 (m, J = 7.8 Hz, 8H; Ar)
Calcd.
81.14
4.38
6.76
7.14 (d, J = 8.4 Hz, 2H; Ar)
Found
78.93
4.36
6.62
%C
%H
%N
4.55 (s, 2H; CH2)
168.5, 153.5, 150.8, 150.3, 145.6, 141.2, 139.9, 136.9 (2C),
130.9 (2C), 128.6 (4C), 128.4 (4C), 128.2, 127.4, 126.6, 126.4,
121.1, 118.9 (2C), 64.9, 50.3
PHY-4
C-H Alif. (2961)
7.92 (m, 4H; Ar)
C-H Alif. (2911)
7.71-7.32 (m, 12H; Ar)
C=O (1783)
7.15 (m, 6H; Ar)
Calcd.
69.40
4.54
5.49
C=O (1719)
6.93 (m, 2H; Ar)
Found
68.55
4.37
5.39
4.56 (s, 4H; CH2)
1.25 (s, 18H; CH3)
6
168.2 (2C), 154.7 (2C), 152.9 (2C), 150.4(2C), 149.4 (2C), 140.9
(4C), 140.8 (4C), 139.5 (2C), 136.5 (2C), 133.1 (2C), 128.5 (q,
1J
C-F = 272.5 Hz, 2C;CF3), 128.2 (6C), 125.9 (6C), 124.8 (2C),
121.2 (2C), 120.6 (q, 2JC-F = 27.9 Hz, 2C;CF3), 118.6 (6C), 63.9,
50.0 (2C), 33.9 (2C), 29.4 (6C)
C59H46F6N4O6
Transmitance (%)
PHY-4
PHY-3
PHY-2
PHY-1
4000
3500
3000
2500
2000
Wavenumbers( cm
1500
-1
1000
500
)
FIGURE S5 ATR-FTIR Spectra of PHYs.
7
d
f e
H2O
c
g
8
a
7
6
5
DMSO
b
4
3
 (ppm)
2
1
0
DMSO
200
180
160
140
120
FIGURE S6 1H and 13C NMR Spectra in DMSO-d6
of PHY-1.
8
100
 (ppm)
80
60
40
20
0
d,h
g
j
c,i
e,f
a
H2O
b
8
7
6
5
4
 (ppm)
DMSO
3
2
1
0
DMSO
200
180
160
140
120
100
 (ppm)
80
60
40
20
0
FIGURE S7 1H and 13C NMR Spectra in DMSO-d6
of PHY-2.
9
b, e f
d
g
9
8
c
a
7
6
5
H2O
4
3
 (ppm)
DMSO
2
1
0
DMSO
200
180
160
140
120
100
 (ppm)
FIGURE S8 1H and 13C NMR Spectra in DMSO-d6
of PHY-3.
10
80
60
40
20
0
b
k,i,l
H2O
e c,j h,d f,g
8
7
DMSO
a
6
5
4
3
 (ppm)
2
1
0
DMSO
200
180
160
140
120
100
 (ppm)
80
60
40
20
0
FIGURE S9 1H and 13C NMR Spectra in DMSO-d6
of PHY-4.
11