New highly phenylated bis(phthalic) and bis(naphthalic) anhydrides and polyimides therefrom - Polyimides and Other High Temperature Polymers - page 99

ethynyl)naphthalic anhydride (0.5966 g, 2 mmol), and 1,2,4-trichlorobenzene
(16 ml). The reaction mixture was boiled for 10 h, cooled, and poured into a 10-fold
excess of methanol. The precipitate was filtered off, dried, and crystallized from
isopropyl alcohol to provide compound III (91%), which did not melt prior to de-

composition.
For C 91 H 58 O 7 , Calcd. (%): C, 87.27; H, 4.37.
Found (%): C, 87.37; H, 4.60.
IR (v, cm -1 ): 1738, 1780 (C=O of naphthalic anhydride), 1658 (C=O of benzo-
phenone group), 1592 (C=C of aromatic ring).
1

, ppm): 6.50-6.60 (m, 8H), 6.60-6.70 (m, 4H), 6.70-6.80
(m, 4H), 6.80-6.98 (m, 28H), 7.03-7.14 (m, 4H), 7.40-7.48 (m, 2H), 7.60-7.66 (m,
2H), 8.22 (d, 2H, J = 8.1 Hz), 8.32 (d, 2H, J=8.1 Hz), 8.42 (d, 2H, J = 8.1 Hz).
13 C NMR (CDC1 3 ,

H NMR (CDC1 3 ,

δ

, ppm): 116.59, 118.27, 125.56, 125.94, 126.05, 126.26,
126.78, 127.78, 128.09, 128.34, 128.44, 128.53, 129.35, 129.76, 129.87,130.49,
130.67, 130.68, 130.97, 131.58, 131.82, 132.26, 134.37, 134.38, 134.59, 135.58,
136.36, 138.87, 138.94, 139.01, 139.16, 139.45, 139.68, 140.24, 140.48, 140.71,
140.81, 140.95, 141.09, 141.62, 144.22, 144.51, 147.47, 147.54 (Ar), 160.33
(-CO-BNA), 160.53 (-CO-BNA), 196.09, 196.14, 196.19 (-CO-benzophenone).

δ

2.2. Polymers
2.2.1. Synthesis of phenylated polyimides

A three-necked flask equipped with a reflux condenser, a stirrer, and an inlet for
feeding argon was charged with dianhydride

VА-VG

II (0.4654 g, 0.5 mmol), p-

phenylenediamine (0.0541 g, 0.5 mmol), and a solution of benzoic acid

(0.1212 g) in m-cresol (10 ml). The latter was used as a catalyst. After the reac-
tion mixture was stirred for 5 h at 180°C, it was cooled and chloroform (2 ml) was
added. The mixture was slowly poured into methanol. The precipitate was washed
several times with methanol and dried at 150°C under vacuum for 20 h. The

IVA

VB-

VG phenylated PIs were prepared in a similar manner.

2.2.2. Synthesis of phenylated poly(naphthalimide)s VIA-VIG

A stirred mixture of equimolar amounts of dianhydride III (0.6678 g, 0.5 mmol)

and p-phenylenediamine (0.0541 g, 0.5 mmol), and p-chlorophenol (1 g) was

heated at 80°C in the presence of benzoic acid (0.09 g) and benzimidazole (0.09
g) in a flow of argon over a 2-h period. After the temperature of the reaction mix-
ture was raised to 140°C, it was stirred for another 5 h and then was slowly
poured into methanol (100 ml). The polymer obtained was filtered off, washed
several times with methanol, and dried under vacuum at 150°C for two days.
The

IVA

VIB-VIG phenylated PNIs were prepared in a similar manner.