Vol. 28, No. 8 (2016)
Study of New Thermally Stable Blue Light Emitting Materials Based Aromatic Polyamides 1741
ammonia was generated. The time taken to reach this stage
was about 24 h. The solution was cooled and the pH value
was adjusted by dil. HCl to around 3. The yellowish precipitate
formed was collected by filtration, washed with water.
Recrystallization from acetic acid gave pale yellow crystals.
By using procedure other monomers (AC2, AC3) were
synthesized (Scheme-I).
Synthesis of poly(amine-amide) (PA1): The poly(amine-
amide) (PA1) was synthesized as follow: A mixture of 1.12 g
(0.03 mol) of the dicarboxylic acid monomer (AC1), 0.32 g
(0.03 mol) of p-phenylenediamine, 0.5 g of calcium chloride,
4.5 mL of triphenyl phosphite (TPP), 1.5 mL of pyridine and
4.5 mL of N-methyl-2-pyrrolidone (NMP) was heated with
stirring at 105 °C for 3 h. The resulting viscous polymer solution
was poured slowly into 300 mL of stirring methanol giving
rise to a stringy fiber-like precipitate that was collected by
filtration, washed thoroughly with hot water and methanol and
dried at 80 °C for 24 h (Scheme-II). The other poly(amine-
amide)s (PA2, PA3) were prepared by above same procedure.
Synthesis of poly(amine-amide) (PAB1): This polymer
Spectral characteristics data
4
,4’-Dicyano-4"-acetyltriphenylamine (CY1): 4.04 g
-1
(
yield: 60 %), m.p. = (188-190) °C, FTIR: 2218 cm , (CN):
1
H NMR (400 MHz, CDCl
Ha), 7.41-7.76 (d, 4H, H ), 7.07-7.23 (d, 4H, H
d, 2H, H ), 2.55 (s, 3H, HCH3). C NMR (400 MHz, CDCl
δ ppm): 150 (C4,5), 108.43 (C ), 118.74 (CN), 125.54 (C
26.02 (C ), 128.21 (C ), 132.38 (C ), 133.61 (C ), 24.73 (CH
,4'-Dicyano-4"-ethyl triphenylamine (CY2): 2.31 g
3
-d1, δ ppm): 7.78-8.12 (d, 2H,
), 6.91-7.07
-d,
),
).
d
c
1
3
(
b
3
(PAB1) was synthesized by the same method, which described
8
6
in synthesis of PA1 but used benzidine instead of p-phenylene
diamine.
1
2
3
7
1
3
4
-1
Spectral characteristics data
(
yield: 71.5 %), m.p. = 167-170 °C. FTIR: 2221 cm (CN),
1
H NMR (400 MHz, CDCl
), 6.89-7.13 (d, 2H, H ), 6.71-6.86 (d, 4H, H
d, 2H, H ), 2.47-2.72 (m, 3H, HCH2), 1.26 (t, 3H, HCH3).
NMR (400 MHz, CDCl -d1, δ ppm): 150.22 (C ), 143.41 (C
42.68 (C ), 132.91 (C ), 128.11 (C ), 127.09 (C ), 123.11
), 118.12 (CN), 108.19 (C ), 28.60 (CCH2), 14.52 (CCH3).
,4'-Dicyano-4"-methoxytriphenylamine (CY3): 2.80
3
-d1, δ ppm): 7.35-7.57 (d, 4H,
Poly(amine-amide) (PA1): The IR spectrum exhibited
H
(
d
a
c
), 6.43-7.71
characteristic amide absorption bands at 3321 (N-H stretching)
13
-1
1
b
C
and 1645 cm (amide carbonyl). H NMR (400 MHz, DMSO-
, δ ppm): 10.25 (S, 1H, HNH-CO), 7.55-7.84 (d, 4H, H ) 7.28-
7.58 (d, 2H, H ), 7.54-7.86 (d, 2H, H ), 6.59-7.89 (d, 4H, H ),
6.59-7.88 (d, 2H, H ), 2.52 (s, 3H, HCH3). C NMR (400 MHz,
DMSO-d , δ ppm): 196.97 (CCO-CH3), 168.84 (C-CO-), 164.77
(CCO-NH), 151.14 (C ), 150.32 (C ), 135.42 (C ), 131.23 (C ),
), 128.63 (C ), 124.94 (C3,6), 122.42 (C11), 116.56
3
5
4
),
d
6
d
1
(
1
7
2
3
e
a
c
13
C
6
8
b
4
6
-1
g (yield: 77.5 %), m.p. = 178-181 °C. FTIR: 2219 cm (CN).
5
4
1
7
1
H NMR (400 MHz, CDCl
), 6.71-6.93 (d, 4H, H ), 6.61-6.53 (d, 2H, H
d, 2H, H ), 3.82 (s, 3H, HCH3), C NMR (400 MHz, CDCl
d1, δ ppm): 157.48 (C ), 150.14 (C ), 138.31 (C ), 134.04 (C
31.87 (C ), 123.58 (C ), 118.06 (CN), 116.33 (C ), 108.54
), 58.73 (CCH3).
,4'-Dicarboxy-4"-isopropyltriphenyl-amine (AC1):
3
-d1, δ ppm): 7.28-7.63 (d, 4H,
129.77 (C
2
9
H
(
d
c
a
), 2.37-2.62
C12), 26.61 (CCH3).
13
b
3
-
Poly(amine-amide) (PA2): Infrared spectrum shows
-
1
-
1
1
5
4
7
),
bands at 3314 cm (N-H stretching) and 1644 cm (amide
1
1
(
3
6
2
carbonyl). H NMR (400 MHz, DMSO-d
1H, HNH-CO), 7.68-7.97 (d, 4H, H ), 7.25-7.44 (d, 2H, He), 6.91-
7.16 (d, 2H, Ha), 6.70-6.98 (d, 4H, Hc), 6.46-6.78 (d, 2H, H ),
), 2.62 (q, 3H, HCH3). C NMR (400 MHz,
, δ ppm): 168.81 (C-CO-), 164.76 (CCO-NH), 151.21
), 146.34 (C ), 144.06 (C13), 134.43 (C ), 131.24.
Poly(amine-amide) (PA3): Infrared spectrum shows bands
6
, δ ppm): 10.25 (S,
C
8
d
4
f
-
1
13
6
.4 g (85 % yields): m.p. = 275-277 °C. FTIR: 1681 cm
6.35-6.66 (d, 2H, H
DMSO-d
(C
b
-1
1
(
C=O), 2987 cm (O-H). H NMR (400 MHz, DMSO-d
ppm): 12.61-12.89 (s, 2H, CCOOH), 7.65-7.97 (d, 4H, H ), 7.56-
.84 (d, 2H, Ha), 6.70-6.98 (d, 4H, H ), 6.58-6.91 (d, 2H,
), 2.55 (s, 3H, HCH3). C NMR (400 MHz, DMSO-d , δ
ppm): 197.22 (CCO-CH3), 168.81 (CCOOH), 151.47 (C5), 150.46
6
, δ
6
d
5
4
1
7
(
C
1
3
-1
-1
H
b
6
at 3304 cm (N-H stretching) and 1644 cm (amide carbonyl).
1
H NMR (400 MHz, DMSO-d
7.68-7.97 (d, 4H, H ), 7.25-7.44 (d, 2H, He), 6.59-6.89 (d,
2H, Ha), 6.70-6.98 (d, 4H, Hc), 6.46-6.78 (d, 2H, H ), 6.38-
), 3.82 (s, 3H, HCH3). C NMR (400 MHz,
, δ ppm): 168.81 (C-CO-), 164.79 (CCO-NH), 151.11
), 144.06 (C13), 136.21 (C ), 132.24 (C ), 131.34 (C ),
128.65 (C ), 124.92 (C ), 124.67 (C ), 122.42 (C11), 116.52
(C12), 115.23 (C ), 55.82 (CCH3).
Poly(amine-amide) (PAB1): The IR spectrum exhibited
6
, δ ppm): 10.25 (S, 1H, HNH-CO),
(
(
C
C
4
), 135.16 (C
), 124.92 (C
,4'-Dicarboxy-4"-ethyltriphenylamine (AC2): 3.40 g
1
), 131.76 (C
7
), 129.13 (C
2
), 124.68 (C
6
) 124.64
d
8
3
), 26.61 (CCH3).
f
13
4
6.68 (d, 2H, H
DMSO-d
(C
b
-
1
(94.18 % yields): m.p. = 276-278 °C. FTIR: 1683 cm (C=O),
6
-
1
1
2
710-3321 cm (O-H). H NMR (400 MHz, DMSO-d
), 6.91-
), 6.46-6.75 (d, 2H,
6
, δ
5
4
3
7
ppm): 12.52-12.91 (s, 2H, CCOOH), 7.67-7.98 (d, 4H, H
.21 (d, 2H, Ha), 6.71-6.97 (d, 4H, H
),, 2.45-2.74 (t, 2H, HCH2), 1.11-1.41 (d, 3H, HCH3). C NMR
400 MHz, DMSO-d , δ ppm): 168.81 (CCOOH), 151.44 (C ),
43.42 (C ), 142.18 (C ), 131.88 (C ), 128.11 (C ), 127.42
), 124.76 (C ), 124.64 (C ), 28.22 (CCH2), 14.61 (CCH3).
,4’-Dicarboxy-4"-methoxytriphenylamine (AC3): 3.40
d
9
6
8
7
C
1
13
(H
b
-
1
(
1
6
5
characteristic amide absorption bands at 3364 cm (N-H
stretching) and 1647 cm (amide carbonyl). H NMR (400
MHz, DMSO-d , δ ppm): 10.25 (s, 1H, HNH-CO), 7.38-8.18 (d,
-1
1
4
1
7
2
(C
3
6
8
6
13
4
12H, He,d,f,a,g), 6.58-6.88 (d, 8H, H,c,b,h), 2.56 (s, 3H, HCH3). C
, δ ppm): 197.00 (CCO-CH3), 164.76
(CCONH), 151.47 (C5), 150.68 (C4), 144.56 (C17), 139.38 (C13),
136.84 (C10), 135.46 (C ), 133.86 (C14), 131.23 (C ), 129.70
(C ), 128.71 (C15), 128.68 (C ), 128.11 (C12), 124.91 (C3,6),
124.62 (C ), 119.81 (C16), 124.71 (C11), 26.63 (CCH3).
Poly(amine-amide) (PAB2): The IR spectrum exhibited
-1
g (94.2 % yield): m.p. = 273-275 °C. FTIR: 1680 cm (C=O),
NMR (400 MHz, DMSO-d
6
-
1
1
2
713-3332 cm (O-H). H NMR (400 MHz, DMSO-d
ppm): 12.76 (s, 2H, HCOOH), 7.68-7.97 (d, 4H, H ), 6.60-6.98
d, 4H, Hc), 6.58-6.89 (d, 2H, Ha), 6.37-6.77 (d, 2H, H ), 3.83
, δ ppm): 168.83
), 138.31 (C ), 132.11 (C ),
), 55.82 (CCH3). Scheme-
6
, δ
d
1
7
(
(
(
b
2
9
13
s, 3H, HCH3). C NMR (400 MHz, DMSO-d
C
6
8
COOH), 157.23 (C
1
), 150.23 (C
5
4
3
-
1
1
31.20 (C
7
), 124.91 (C
6
), 115.34 (C
2
characteristic amide absorption bands at 3364 cm (N-H
-1
1
I shows the routes of synthesis.
stretching) and 1648 cm (amide carbonyl). H NMR (400 MHz,