Imide-Containing Ladder Polyphenylsilsesquioxanes
with High Thermal Stability and Thermoplastic
Properties
Ricardo Chavez, Emanuel Ionescu*, Claudia Fasel, and Ralf Riedel
Institut für Materialwissenschaft, Technische Universität Darmstadt, Petersenstrasse 32, 64287
Darmstadt, Germany, ionescu@materials.tu-darmstadt.de
Supporting Information
NH2
HN
Boc
a.
b.
HN Boc
2
Cl
+
Si Cl
Cl
Br
Br
Li
(I)
(II)
c.
Si
Boc
H2N
NH2 Boc
H
N
Si
N
H
Cl
H
N Boc
(III)
d.
Si
f.
O
e.
O
Si
N Boc
H
Si
H2N
NH2
Boc
N Boc
H
N
H
Si
(VI)
(V)
O
Boc=
C O
Boc
N
H
OH
(IV)
N Boc
H
a. Boc2O / H2O / RT
b. BuLi / THF / Hexane /-80°C
c. THF / Hexane / -80 °C
d. H2O
e. RT
f. TFA / Toluene / RT
Figure S1. Synthesis approach for the monomers (VI)
1. Monomer Synthesis
1a. Spectroscopic data of (I)
 tert-Butyl-N-(4-bromophenyl)carbamate (white powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 1.37 (s, 9H, -CH3); 7.23 (d, 2H, Phenyl); 7.29 (d, 2H,
Phenyl); 8.43 (s, 1H, -NH-); 13C (500MHz, THF-d8): δ (ppm)= 28 (-CH3); 79 (-C-); 115 (Phenyl CBr); 121 (Phenyl CH); 132 (Phenyl CH); 140 (Phenyl C-NH-); 154 (-C=O).
FT-IR: ν (cm-1)= 3367 (s, -NH); 2979 (s, -CH3); 1696 (s, -C=O); 1068 (s, -Br).
 tert-Butyl-N-(3-bromophenyl)carbamate (brown powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 1.5 (s, 9H, -CH3); 7.09 (te, 2H, Phenyl); 7.31(d, 1H, Phenyl);
7.81 (s, 1H, Phenyl); 8.6(s, 1H, -NH-); 13C (500MHz, THF-d8): δ (ppm)= 26 (-CH3); 78(-C-); 114
(Phenyl CH); 119 (C-Br); 120 (Phenyl CH); 123 (Phenyl CH); 128 (Phenyl CH), 139 (Phenyl C-NH-);
150.9 (-C=O).
FT-IR: ν (cm-1)= 3309 (s, -NH-); 2975 (s, -CH3); 1609 (s, -C=O); 1068 (s, Phenyl C-Br)
SI-1
1b. Spectroscopic data of (III)
 Chlorophenyl-bis(4-(tert-butylcarbamate-N-yl)phenyl)silane (white powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 1.36 (s, 18H, -CH3); 6.93 (d, 3H, Phenyl CH); 7.29 (te, 6H,
Phenyl CH); 7.8 (d, 4H, Phenyl CH); 8.59 (s, 2H, -NH-); 13C (500MHz, THF-d8): δ (ppm)= 28 (-CH3);
83 (-C-); 120 (Phenyl CH); 128 (Phenyl CH); 132 (Phenyl CH); 136 (Phenyl C-Si-); 140 (Phenyl CNH-); 156(-C=O); 29Si (500MHz, THF-d8): δ (ppm)= -25.
FT-IR: ν (cm-1)= 3417 (s, -NH-); 2977 (s, -CH3); 1698 (s, C=O); 1430 (s, Si-C Phenyl); 1120 (w, Si-C
Phenyl); 700 (s, Si-C Phenyl).
 Chlorophenyl-bis(3-(tert-butylcarbamate-N-yl)phenyl)silane (white powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 1.36 (s, 18H, -CH3); 6.96 (te, 2H, Phenyl CH); 7.25, (te, 5H,
Phenyl CH); 7.48 (d, 2H, Phenyl CH); 7.73 (d, 2H, Phenyl CH); 7.84 (d, 2H, Phenyl CH); 8.66 (s, 2H,
-NH-); 13C (500MHz, THF-d8): δ (ppm)= 28 (-CH3); 82 (-C-); 122 (Phenyl C-Si-); 124 (Phenyl CH);
128 (Phenyl CH); 130 (Phenyl CH); 133 (Phenyl CH); 135 (Phenyl CH); 141 (Phenyl C-NH-); 155(C=O); 29Si (500MHz, THF-d8): δ(ppm)= -25.
FT-IR: ν (cm-1)= 3331(s, -NH-); 2975 (s, -CH3); 1732 (s, C=O); 1428 (m, Si-C Phenyl); 1153 (w, SiC Phenyl); 694 (s, Si-C Phenyl).
1c. Spectroscopic data of (V)
 1,1,3,3-Tetra-(4-(tert-butylcarbamate-N-yl)phenyl)-1,3-diphenyldisiloxane (pink powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 1.42 (s, 36H, -CH3); 7.25 (d, 14H, Phenyl CH); 7.35 (d, 12H,
Phenyl CH); 8.56 (s, 4H, -NH-); 13C (500MHz, THF-d8): δ (ppm)= 26 (-CH3); 77.5 (-C-); 112 (Phenyl
CH); 118 (Phenyl CH);126 (Phenyl CH);130 (Phenyl CH); 132 (Phenyl C-Si-);138 (Phenyl
C-NH-);151.5 (-C=O); 29Si (500MHz, THF-d8): δ (ppm)= -80.
FT-IR: ν (cm-1)= 3367 (s, -NH-); 2982 (s, -CH3); 1696 (s, C=O); 1430 (s, Si-C Phenyl); 1120 (m, Si-C
Phenyl); 1050 (s, Si-O); 700 (s, Si-C Phenyl).
 1,1,3,3-Tetra-(3-(tert-butylcarbamate-N-yl)phenyl)-1,3-diphenyldisiloxane (red-pink powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 1.43 (s, 36H, -CH3); 6.98 (te, 14H, Phenyl CH); 7.29 (d, 4H,
Phenyl CH); 7.82 (s, 8H, Phenyl CH); 8.67(s, 4H, -NH-); 13C (500MHz, THF-d8): δ (ppm)= 26 (CH3); 78 (-C-); 114 (Phenyl CH); 120 (Phenyl CH); 123 (Phenyl CH);125 (Phenyl CH); 128 (Phenyl
CH); 132 (Phenyl C-Si-); 140 (Phenyl C-NH-); 51 (-C=O); 29Si (500MHz, THF-d8): δ (ppm)= -80.
FT-IR: ν (cm-1)= 3421 (s, -NH-); 2973 (s, - CH3); 1691 (s, C=O); 1430 (s, Si-C Phenyl); 1125 (m, SiC Phenyl); 1056 (s, -Si-O); 697 (s, Si-C Phenyl).
1d. Spectroscopic data of (VI)
 1,1,3,3-Tetra-(4-aminophenyl)-1,3-diphenyldisiloxane (red-pink powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 6.7 (d, 8H, -NH2); 7.16 (d, 14H, Phenyl CH); 7.72 (s, 12H,
Phenyl CH); 13C (500MHz, THF-d8): δ(ppm)= 109 (Phenyl CH); 116 (Phenyl CH); 128 (Phenyl CH);
132 (Phenyl CH); 134 (Phenyl C-Si-); 147 (Phenyl C-NH2); 29Si (500MHz, THF-d8): δ (ppm)= -80.
FT-IR: ν (cm-1)= 3600 (m, -NH2); 3385 (s, -NH2); 1430 (s, Si-C Phenyl); 1130 (s, Si-C Phenyl); 1068
(s. Si-O); 700 (s, Si-C Phenyl).
SI-2
MS (ESI, 76 eV): m/z = 93 ([C6H5-NH2]+), 230 ([O-Si(C6H5NH2)2]+, 533 ([(C6H5)6Si2O]+), 577
([(C6H5NH2)3(C6H5)3Si2O]+).
Elemental Analysis (wt%): C 72.5 (calc.: 72.69), H 5.8 (5.76), N 9.4 (9.42), O 2.7 (2.69), Si 9.4
(9.44).
 1,1,3,3-Tetra-(3-aminophenyl)-1,3-diphenyldisiloxane (red-pink powder)
NMR: 1H (500MHz, THF-d8): δ (ppm)= 6.42 (d, 8H, -NH2); 6.57 (d, 8H, Phenyl CH); 6.70 (s,
8H, Phenyl CH); 6.79 (t, 10H, Phenyl CH); 13C (500MHz, THF-d8): δ (ppm)= 114
(Phenyl
CH); 118 (Phenyl CH); 120 (Phenyl CH); 123 (Phenyl C-Si-); 127 (Phenyl CH); 130 (Phenyl
CH); 134 (Phenyl CH); 149 (Phenyl C-NH2); 29Si (500MHz, THF-d8): δ (ppm)= -80.
FT-IR: ν (cm-1)= 3399 (m, -NH2); 3071 (s, -NH2); 1432 (s, Si-C Phenyl); 1135 (s, Si-C Phenyl);
1068 (s. Si-O); 691 (s, Si-C Phenyl).
2. Polymer Synthesis
2a. Spectroscopic data of LA01-p (yellow powder)
O
Si
N
N
O
O
O
Si
O
O
O
N
N
O
O
n
FT-IR: ν (cm-1)= 1777 (m, Imide); 1720 (s, -C=O); 1435 (m, Si-C Phenyl); 1113 (s, Si-C Phenyl);
1067 (s, Si-O); 708 (s, Si-C Phenyl).
Melting Point (°C)= Does not melt.
Degradation Temperature (°C)= 421 (determined by means of TGA)
2b. Spectroscopic data of LA01-m (yellow powder)
O
O
N
N
Si
O
O
O
O
O
Si
N
N
O
O
n
SI-3
FT-IR: ν (cm-1)= 1774 (m, Imide); 1721 (s, -C=O); 1435 (m, Si-C Phenyl); 1113 (s, Si-C Phenyl);
1070 (m, Si-O); 703 (m, Si-C Phenyl).
Melting Point (°C)= Does not melt.
Degradation Temperature (°C)= 400 (TGA).
2c. Spectroscopic data of LA02-p (yellow powder)
O
Si
O
N
N
O
O
O
Si
O
O
O
O
N
N
O
O
n
FT-IR: ν (cm-1)= 1781 (m, Imide); 1720 (s, -C=O); 1491 (m, Si-C Phenyl); 1120 (m, Si-C Phenyl);
1012 (m, Si-O); 710 (s, Si-C Phenyl).
EA: C 72.4 (calc. 72.41), H 4.1 (4.11), N 4.6 (4.56), O 14.3 (14.34), Si 4.6 (4.58).
Melting Point (°C)= 405.
Degradation Temperature (°C)= 460 (TGA).
2d. Spectroscopic data of LA02-m (white powder)
O
O
O
N
N
Si
O
O
O
O
Si
O
O
N
N
O
O
n
FT-IR: ν (cm-1)= 1779 (m, Imid); 1723 (s, -C=O); 1428 (m, Si-C Phenyl); 1130 (s, Si-C Phenyl); 1077
(s, Si-O); 697 (m, Si-C Phenyl).
Melting Point (°C)= 200
Degradation Temperature (°C)= 361 (TGA).
SI-4
2e. Spectroscopic data of LA03-p (white powder)
O
O
O
Si
N
N
O
O
O
O
O
O
N
N
Si
O
O
n
FT-IR: ν (cm-1)= 1777 (m, Imide); 1723 (s, -C=O); 1430 (m, Si-C Phenyl); 1237 (m, C-O-C); 1130 (s,
Si-C Phenyl); 1068 (s, Si-O); 697 (m, Si-C Phenyl).
Melting Point (°C)= 235.
Degradation Temperature (°C)= 358 (TGA).
2f. Spectroscopic data of LA03-m (white powder)
O
O
O
N
N
Si
O
O
O
O
O
Si
O
N
N
O
O
n
FT-IR: ν (cm-1)= 1779 (m, Imide); 1718 (s, -C=O); 1428 (m, Si-C Phenyl); 1237 (m, C-O-C); 1133 (s,
Si-C Phenyl); 1032 (m, Si-O); 697 (m, Si-C Phenyl).
Melting Point (°C)= 200.
Degradation Temperature (°C)= 323 (TGA).
SI-5
3. Thermal properties of the synthesized polymers (VI)
100
80
80
70
70
60
50
40
60
50
40
30
30
20
20
10
200
300
400
500
600
700
800
LA02-p
LA02-m
90
Mass m [%]
Mass m [%]
100
LA01-p
LA01-m
90
10
900
200
300
Temperature T [°C]
400
500
600
700
800
900
Temperature T [°C]
a)
b)
100
LA03-p
LA03-m
90
Mass m [%]
80
70
60
50
40
30
20
10
200
300
400
500
600
700
800
900
Temperature T [°C]
c)
Figure S2. TGA curves for a) pyromellitic-dianhydride-based ladder polymers (LA01-p and LA01m), b) BTDA-based ladder polymers (LA02-p and LA02-m), and c) OPDA-based ladder polymers
(LA03-p and LA03-m).
100
100
90
80
50
Under Ar
40
30
Mass m [%]
Mass m [%]
60
Under O2
90
85
20
10
0
Under Ar
95
70
Under O2
200
300
400
500
600
700
Temperature T [°C]
800
900
80
150
200
250
300
350
400
450
500
Temperature T [°C]
Figure S3. TGA curves of LA02-p upon heating in Argon and Oxygen atmospheres.
SI-6