Polyamidoimides with pendent chromophores
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 6, June, 2005
1487
was 26.6 g (73%), bright orange crystals, m.p. 153—154 °C.
Found (%): C, 61.64; H, 6.42; N, 12.50; O, 19.44. C15H13N3O4.
Calculated (%): C, 61.62; H, 6.39; N, 12.68; O, 19.31. 1H NMR
(CDCl3), δ: 2.79 (m, 1 H, H(5″)); 2.96 (m, 1 H, H(4″)); 3.40
(m, 1 H, H(3″)); 4.05 (m, 1 H, H(2″)); 4.87 (m, 1 H, H(1″));
7.92 (d, 2 H, H(2), H(6), J = 8.4 Hz); 7.92 (d, 2 H, H(3), H(5),
J = 8.4); 7.99 (d, 2 H, H(2´), H(6´), J = 9.3 Hz); 8.35 (d, 2 H,
H(3´), H(5´), J = 9.3 Hz).
Glycidyl ether of 4ꢀ(6ꢀnitrobenzothiazolꢀ2ꢀylazo)phenol (4)
was synthesized similarly from phenol 2. The yield was 52%,
reddishꢀbrown crystals, m.p. 160 °C. Found (%): C, 55.59;
H, 5.23; N, 14.40; O, 16.44; S, 8.34. C15H12N4O4S. Calcuꢀ
lated (%): C, 55.66; H, 5.19; N, 14.42; O, 16.48; S, 8.25.
1H NMR (DMSOꢀd6), δ: 2.72—2.97 (m, 1 H, H(5″)); 3.32—3.50
(m, 1 H, H(4″)); 3.64—3.89 (m, 1 H, H(3″)); 4.14—4.64 (m,
2 H, H(1″), H(2″)); 6.48 (d, 2 H, H(2), H(6), J = 8.6 Hz); 7.56
(d, 2 H, H(3), H(5), J = 8.6 Hz); 8.08 (d, 1 H, H(4´), J =
8.5 Hz); 8.30 (d, 1 H, H(5´), J = 8.5 Hz); 8.77 (s, 1 H, H(7´)).
PAI was modified with glycidyl ethers of azo dyes according
to a known procedure.10
7.6 Hz); 7.95—8.70 (m, 13 H, H(1), H(2), H(3), H(4), H(5),
H(6), H(7), H(8), H(9), H(3″), H(5″), H(4″′), H(5″′)); 9.22 (s,
1 H, H(7″′)); 10.73 (s, 2 H, NH).
This work was financially supported by the Council on
Grants of the President of the Russian Federation (State
Program for Support of Leading Scientific Schools, Grant
No. NShꢀ1824.2003.3) and the St. Petersburg Scientific
Center of the Russian Academy of Sciences (Grants "Synꢀ
thesis and Photophysical Properties of MetalꢀPolymer
Complexes Based on Polymers with Ligands in Side
Chain" and "Synthesis of New Soluble Thermally Stable
Polymeric Brushes by Living Radical Polymerization of
ChromophoreꢀContaining Methacrylates on a Polyimide
Initiator," 2005).
References
1. I. E. Kardash and A. V. Pebalk, Itogi Nauki i Tekhniki.
Khimiya i Tekhnologiya Vysokomolekulyarnykh Soedinenii
[Results of Science and Technology. Chemistry and Technology
of HighꢀMolecular Compounds], 1990, 26, 88 (in Russian).
2. D. M. Burland, R. D. Miller, and C. A. Walsh, Chem. Rev.,
1994, 94, 31.
3. T.ꢀA. Chen and A. K. Jen, Macromolecules, 1996, 29, 535.
4. B. Z. Motsenyat, V. A. Gusinskaya, and M. M. Koton,
Plastmassy [Plastics], 1981, 6, 55 (in Russian).
5. V. A. Gusinskaya, S. S. Churganova, and M. M. Koton,
Zh. Prikl. Khim., 1984, 57, 1819 [J. Appl. Chem. USSR, 1984,
57 (Engl. Transl.)].
Modification of PAI with glycidyl ether 3. Glycidyl ether of
4ꢀ(4ꢀnitrophenylazo)phenol (3) (4.85 g, 0.016 mol) and DMBA
(0.145 g, 0.0011 mol, 3% of the chromophore mass) were added
with stirring to a solution of PAI (4.7 g, 0.008 mol) in NMP
(180 mL) at 60 °C. The reaction mixture was stirred for 2—30 h
at 60 °C (see Table 1). The modified polymer was isolated by
precipitation with water. The precipitated polymer was filtered
off and dried, and unconsumed chromophore was extracted with
acetone in a Soxhlet apparatus for 48 h. PAIꢀ1 was obtained.
n : m = 15 : 85. Found (%): C, 63.89; H, 4.21; N, 9.93; O, 21.97.
(C46H38N7O12 0.15
H, 4.17; N, 9.97; O, 22.02. n : m = 30 : 70. Found (%): C, 63.55;
H, 4.17; N, 10.27; O, 22.01. (C46H38N7O12 0.3(C31H24N4O8)0.7
)
(C31H24N4O8)0.85. Calculated (%): C, 63.84;
6. W. Wrasidlo and J. M. Augl, J. Polym. Sci., 1969, P. Aꢀ1,
7, 1589.
)
.
Calculated (%): C, 63.58; H, 4.21; N, 10.24; O, 21.97.
7. M. S. Malinovskii, Okisi olefinov i ikh proizvodnye [Olefin
Oxides and Their Derivatives], GNIIKhL, Moscow, 1961,
963 (in Russian).
n : m = 50 : 50. Found (%): C, 63.35; H, 4.26; N, 10.51;
O, 21.88. (C46H38N7O12)0.5(C31H24N4O8)0.5. Calculated (%):
C, 63.29; H, 4.24; N, 10.55; O, 21.92. n : m = 90 : 10.
8. S. K. Kurtz, J. Jerphagnon, and M. M. Choy, Landoltꢀ
Bornstein Numerical Data and Functional Relationships in
Science and Technology, Springer, New York, 1979, 11, 671.
9. J. J. P. Stewart, Comput. Chem., 1989, 10, 209.
10. M. Ya. Goikhman and K. A. Romashkova, Zh. Prikl. Khim.,
1999, 72, 473 [Russ. J. Appl. Chem., 1999, 72, 493 (Engl.
Transl.)].
Found (%): C, 62.79; H, 4.29; N, 11.08; O, 21.84.
(C46H38N7O12)0.9(C31H24N4O8)0.1. Calculated (%): C, 62.82;
H, 4.31; N, 11.04; O, 21.83. 1H NMR (DMSOꢀd6), δ: 1.35 (s,
4 H, H(12), H(13)); 1.62 (s, 4 H, H(11), H(14)); 3.60 (m, 4 H,
H(10), H(15)); 3.84—4.42 (m, 5 H, H(1´), H(2´), H(3´)); 7.16
(d, 2 H, H(2″), H(6″), J = 7.0 Hz); 7.95—8.70 (m, 15 H, H(1),
H(2), H(3), H(7), H(8), H(9), H(4), H(5), H(6), H(3″), H(5″),
H(3″′), H(5″′), H(2″′), H(6″′)); 10.73 (s, 2 H, NH).
11. B. I. Stepanov, Vvedenie
v khimiyu i tekhnologiyu
organicheskikh krasitelei [Introduction to the Chemistry and
Technology of Organic Dyes], Khimiya, Moscow, 1971, 231
(in Russian).
Modification of PAI with glycidyl ether 4. PAIꢀ2 modified
with chromophore 4 was obtained using a similar procedure.
n : m = 20 : 80. Found (%): C, 63.02; H, 4.13; N, 10.29;
O, 21.58; S, 0.98. (C46H38N7O12S)0.2(C31H24N4O8)0.8. Calcuꢀ
lated (%): C, 63.00; H, 4.08; N, 10.32; O, 21.61; S, 0.99.
1H NMR (DMSOꢀd6), δ: 1.35 (s, 4 H, H(12), H(13)); 1.62 (s,
4 H, H(11), H(14)); 3.60 (m, 4 H, H(10), H(15)); 2.84—4.52
(m, 5 H, H(1´), H(2´), H(3´)); 7.16 (d, 2 H, H(2″), H(6″), J =
12. Yu. G. Egorenkov and N. Yu. Rumyantseva, Pat. USSR
1618746; Chem. Abstrs, 1991, 115, P8557a.
Received May 11, 2004;
in revised form April 19, 2005