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for 15 h, cooled to room temperature, and poured in water
(500 mL) to gain a yellowish precipitate. This obtained solid
was further purified by recrystallization from ethanol.
2,20-Sulfide-bis(4-chloro-1-(4-nitrophenoxy) Phenyl Ether
(2a)
Yield: 12.66 g (96%). M.p.: 135–137 8C. 1H NMR (500 MHz,
CDCl3, d): 8.14 (d, 4H, J 5 9.2 Hz, He), 7.15 (m, 4H, Ha and
Hb), 6.97 (d, 2H, J 5 5.0 Hz, Hc), 6.83 (d, 4H, J 5 9.2 Hz, Hd);
13C NMR (125 MHz, CDCl3, d): 168.1 (C7), 156.1 (C6), 147.7
(C10), 135.4 (C2), 131.9 (C3), 130.9 (C9), 127.0 (C4), 119.2
(C1), 118.4 (C5), 114.5 (C8); IR (KBr): m 5 3026 (w, ArAH
stretching), 1606, 1587 (s, asymmetrical nitro stretching),
1526, 1475, 1353 (s, symmetrical nitro stretching), 1262,
1243, 1201, 1162, 1144, 1088, 1058, 897, 865, 824,
783,737, 693, 656 cm21. Anal. Calcd. for C24H14Cl2N2O6S
(%): C 54.45, H 2.67, N 5.29; found, C 54.40, H 2.65, N 5.27.
SCHEME 1 Synthesis of the diamine monomers.
2,20-Sulfoxide-bis(4-chloro-1-(4-nitrophenoxy) Phenyl
Ether (2b)
2,20-Sulfoxide-bis(4-chloro-1-(4-aminophenoxy) Phenyl
Ether (3b)
Yield: 25.5 g (94%). M.p.: 208–210 8C. 1H NMR (500 MHz,
CDCl3, d): 8.26 (d, 4H, J 5 10.2 Hz, He), 8.01 (d, 2H, J 5 1.6 Hz,
Ha), 7.54 (dd, 2H, J 5 8.8, 1.6 Hz, Hb), 7.36 (d, 2H, J 5 8.8 Hz,
Hc), 7.20 (d, 4H, J 5 10.2 Hz, Hd); 13C NMR (125 MHz, CDCl3,
d): 160.8 (C7), 150.4 (C6), 141.2 (C10), 129.6 (C4), 129.2 (C2),
127.5 (C3), 124.6 (C9), 123.2 (C5), 121.9 (C1), 116.9 (C8); IR
(KBr): m 5 3025 (w, ArAH stretching), 1642, 1604, 1565 (s,
asymmetrical nitro stretching), 1532, 1490, 1362 (s, sym-
metrical nitro stretching), 1345, 1265, 1205, 1086, 917, 804,
670 cm21. Anal. Calcd. for C24H14Cl2N2O7S (%): C 52.86, H
2.94, N 5.14; found, C 52.84, H 2.96, N 5.13.
Yield: 3.75 g (77%). M.p.: 129–131 8C. 1H NMR (500 MHz,
CDCl3, d): 7.96 (d, 2H, J 5 1.5 Hz, Ha), 7.54 (dd, 2H, J 5 9.0,
1.5 Hz, Hb), 7.30 (d, 2H, J 5 9.0 Hz, Hc), 6.75 (d, 4H,
J 5 10.2 Hz, Hd), 6.71 (d, 4H, J 5 10.2 Hz, He), 4.75–5.23
(broad, NH); 13C NMR (125 MHz, CDCl3, d): 153.4 (C6), 143.7
(C7), 136.5 (C10), 129.4 (C4), 129.2 (C2), 127.5 (C3), 123.26
(C9), 121.9 (C1), 121.6 (C5), 115.8 (C8); IR (KBr): m 5 3455
(s, NAH stretching), 3348 (m, NAH stretching), 3036 (w,
ArAH stretching), 1623 (m, NAH bending), 1500, 1486,
1447, 1336, 1273, 1230, 1200, 1125, 1038, 838 cm21. Anal.
Calcd. for C24H18Cl2N2O3S (%): C, 59.39; H, 3.74; N, 5.77;
found, C, 59.37; H, 3.80; N, 5.68.
Synthesis of Diamine Monomers
General Polymerization Procedure
A 200-mL round-bottom flask was charged with a mixture of
dinitro intermediate 2a or 2b (10 mmol), 100 mL dry metha-
nol, Zn (25 mmol, 1.63 g), and ammonium chloride (32
mmol, 1.71 g). The reaction mixture was heated to reflux
temperature and maintained at this temperature for 14 h.
Then, the reaction mixture was cooled to ambient tempera-
ture, filtered, and poured into 500 mL water. The white pre-
cipitate was filtered, dried, and recrystallized from ethanol.
All polymerizations were carried out in a nitrogen atmos-
phere and a representative example is as follows: 3a (5
mmol, 2.347 g,), 1.1 mL of TPP, 1.2 mL of pyridine, and 7 mL
of freshly distilled NMP were charged in a 20-mL flask
equipped with a magnetic stirrer, a nitrogen inlet, and an oil
bath. After dissolving 3a, terephthalic acid (5 mmol, 0.830 g)
and 0.9 g of LiCl was added and heated at 110 8C for 4 h
under nitrogen atmosphere to yield a viscous solution. Usu-
ally after 2 h the reaction solution became too viscous and
additional 2 mL of NMP was added. At the end of the reac-
tion, the polymer solution was poured slowly into 200 mL of
methanol under rapid stirring. The stringy polymer was fil-
tered, washed thoroughly with hot water (2 3 100 mL) and
methanol (2 3 100 mL), and dried under vacuum at 100 8C
overnight. Further purification was carried out by dissolving
the polymer in DMAc or dimethylsulfoxide (DMSO), filtering
the polymer solution, and then precipitating it into methanol.
The inherent viscosity of this polymer in DMAc was 0.84 dL
g21, measured at a concentration of 0.5 g dL21 at 30 8C.
Yield: 93%. 1H NMR (500 MHz, DMSO-d6, d): 10.03–10.14
(broad, NH), 8.04 (4H, Hg), 7.52 (d, 2H, J 5 1.4 Hz, Ha), 7.35
(dd, 2H, J 5 8.1, 1.4 Hz, Hb), 6.86 (m, 6H, Hc and Hd), 6.72 (d,
2,20-Sulfide-bis(4-chloro-1-(4-aminophenoxy) Phenyl Ether
(3a)
Yield: 3.61 g (75%). M.p.: 124–126 8C. 1H NMR (500 MHz,
CDCl3, d): 7.43 (d, 2H, J 5 1.4 Hz, Ha), 7.26 (dd, 2H, J 5 8.2,
1.4 Hz, Hb), 6.81 (m, 6H, Hc and Hd), 6.67 (d, 4H, J 5 8.8 Hz,
He), 4.43–5.61 (broad, NH); 13C NMR (125 MHz, CDCl3, d):
148.4 (C6), 142.2 (C7), 134.8 (C10), 132.7 (C2), 128.2 (C3),
127.4 (C4), 125.9 (C1), 119.0 (C5), 116.9 (C9), 113.9 (C8); IR
(KBr): m 5 3450 (m, NAH stretching), 3342 (w, ArAH
stretching), 3029 (w, ArAH stretching), 1628 (m, NAH bend-
ing), 1500, 1483, 1450, 1343, 1275, 1232, 1214, 1129, 1043,
835 cm21. Anal. Calcd. for C24H18Cl2N2O2S (%): C, 61.41; H,
3.87; N, 5.97; found, C, 61.39; H, 3.89; N, 5.93.
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2015, 53, 2867–2877
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