Polyamidoimides with side chromophoric groups

Article abstract of DOI:10.1007/s11172-005-0431-0

A new method was elaborated for the introduction of chromophores into the side chains of polymers by esterification of polyamidoimides containing side carboxy groups with glycidyl ethers of dyes, 4-(4-nitrophenylazo)phenol and 4-(6-nitrobenzothiazol-2-ylazo)phenol. The optimum modification conditions were found that made it possible to esterify 15, 30, 50, and 90% of the carboxy groups. The synthesized polymers possess valuable physicomechanical properties (E = 2.8-3.3 GPa, σ_u = 69-90 MPa, ε_u = 38-77%) and glass transition temperatures of 115-125°C, depending on the degree of esterification. After chromophore orientation in the corona discharge, all the polymers demonstrate nonlinear optical properties of the second order.

Full text of DOI:10.1007/s11172-005-0431-0

Russian Chemical Bulletin, International Edition, Vol. 54, No. 6, pp. 1481—1487, June, 2005
1481
Polyamidoimides with side chromophoric groups
a
a
a
a
b
M. Ya. Goikhman,a L. I. Subbotina, I. V. Gofman, A. V. Yakimanskii, A. E. Bursian, V. A. Lukoshkin,
ꢀ
G. N. Fedorova,a A. V. Sidorovich,a O. E. Praslova,a N. N. Smirnov,a I. V. Abalov,a and V. V. Kudryavtseva
aInstitute of Macromolecular Compounds, Russian Academy of Sciences,
31 Bol´shoi prosp., 199004 St. Petersburg, Russian Federation.
Fax: +7 (812) 323 6869. Eꢀmail: goikhman@hq.macro.ru
bA. I. Ioffe Physical Technical Institute, Russian Academy of Sciences,
26 ul. Politekhnicheskaya, 194021 St. Petersburg, Russian Federation.
Fax: +7 (812) 247 1017. Eꢀmail: post@pop.ioffe.rssi.ru
A new method was elaborated for the introduction of chromophores into the side chains of
polymers by esterification of polyamidoimides containing side carboxy groups with glycidyl
ethers of dyes, 4ꢀ(4ꢀnitrophenylazo)phenol and 4ꢀ(6ꢀnitrobenzothiazolꢀ2ꢀylazo)phenol. The
optimum modification conditions were found that made it possible to esterify 15, 30, 50, and
90% of the carboxy groups. The synthesized polymers possess valuable physicomechanical
properties (E = 2.8—3.3 GPa, σu = 69—90 MPa, εu = 38—77%) and glass transition temperaꢀ
tures of 115—125 °C, depending on the degree of esterification. After chromophore orientation
in the corona discharge, all the polymers demonstrate nonlinear optical properties of the
second order.
Key words: polymers, chromophores, nonlinear optics.
The creation of polymers with nonlinear optical propꢀ
erties is an urgent task of the modern polymer chemistry,
because these materials play the key role in solution of the
problem of the interaction of laser radiation with the matꢀ
ter, which changes the characteristics of the incident laser
radiation.1 Two main schemes for the synthesis of polyꢀ
mers with side chromophoric groups are presently used:
(1) synthesis of polymers with side reactive groups (for
instance, with carboxy, amino, or hydroxy groups) folꢀ
lowed by modification2; (2) synthesis of monomers conꢀ
taining chromophoric groups and their conversion into
polymers.3
In both cases, researchers face some difficulties. In
the former case, the problems are related to usually low
rates and degrees of polymer modification. As for the
latter approach, the synthesis of chromophoreꢀcontainꢀ
ing monomers is a rather difficult problem.
In the framework of the former approach, we develꢀ
oped a new method for the introduction of chromophores
into the side chains of polymers by esterification of polyꢀ
mers containing side carboxy groups with glycidyl ethers
of dyes. Polyamidoimides (PAI) were chosen as the polyꢀ
meric matrices. These polymers find wide use in microꢀ
electronics due to their solubility in amide solvents and
fairly good physicomechanical, thermophysical, and diꢀ
electric properties.4,5 The most popular method for the
synthesis of PAI is the reaction of imidodicarboxylic acid
dichlorides with aromatic diamines.6 In the present work,
we synthesized PAI from 3,5ꢀdiaminobenzoic acid and
di(trimellitimidic acid) dichloride with a hexamethylene
bridge. The use of 3,5ꢀdiaminobenzoic acid as a monoꢀ
mer allows one to modify the polymer synthesized. The
epoxy group is known to be highly reactive and reacts
easily with the carboxy group to form an ester bond. The
purpose of the present work is to synthesize PAI and
glycidyl ethers of azo dyes and to study the process of
modification of PAI with these glycidyl ethers and the
properties of the synthesized polymers.
Results and Discussion
The starting carboxylꢀcontaining polymer PAI was
synthesized according to Scheme 1 and modified using
the reaction with glycidyl ethers of azo dyes. The choice
of dyes for the polymeric matrix modification is deterꢀ
mined by the following requirements: the required comꢀ
pound should contain the donor and acceptor groups
linked through a conjugation chain and the absorption
maxima of the chromophores should be in the wavelength
region not shorter than 300 nm. In addition, the molecule
should contain a reactive hydroxy group. Dyes 1 and 2
containing the hydroxy group as a donating substituent
and the withdrawing nitro group meet these requirements.
They were synthesized by the azocoupling reaction
(Scheme 2).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1438—1444, June, 2005.
1066ꢀ5285/05/5406ꢀ1481 © 2005 Springer Science+Business Media, Inc.

1482
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 6, June, 2005
Goikhman et al.
Scheme 1
Scheme 2
for the synthesis consisting of the reaction of hydroxylꢀ
containing dyes with epichlorohydrin in the presence of a
catalyst (katamine). This method allows the reaction to
be carried out under mild conditions to form ethers 3
and 4 in high yields (Scheme 3).
Scheme 3
The reaction of αꢀoxide compounds with carboxylic
acids has been known long ago (see, e.g., Ref. 7). The
synthesized glycidyl ethers reacted with the carboxy
groups of PAI in the presence of a catalyst, viz., dimethylꢀ
benzylamine (DMBA) or dicyclohexyl peroxydicarbonate
(CPC), in Nꢀmethylpyrrolidone (NMP). For a strong
nonlinear optical response it is sufficient that the degree
of modification of the polymer with side chromophoric
groups was 50%. This value was chosen as a reference for
selecting modification conditions. Our studies showed that
the use of more than twofold molar excess of the glycidyl
Glycidyl ethers of the synthesized dyes should be preꢀ
pared in the next stage. Such ethers are known to be the
most convenient for the modification of polymers conꢀ
taining carboxy groups in the side chains. The synthesis of
glycidyl ethers is usually rather difficult. As a rule, they
are prepared by ring closure in a strongly alkaline medium
at high temperatures. In our case, this approach is inapꢀ
propriate, because azo compounds are unstable in conꢀ
centrated alkalis. Therefore, we developed a new method

Polyamidoimides with pendent chromophores
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 6, June, 2005
1483
Table 1. Degree of modification of PAI with chromophore 3 under different reaction conditions
T
/°C
3 : COOH*
Cataꢀ
lyst
Degree of modification after t**/h
2
4
6
12
18
24
30
40
60
80
60
40
2 : 1
2 : 1
2 : 1
1 : 1
2 : 1
DMBA
DMBA
DMBA
DMBA
CPC
—
—
4.8
40.0
66.6
25.7
14.3
—
13.3
74.3
90.0
38.1
—
29.5
84.8
—
40.9
—
33.3
89.5
—
58.1
—
25.7
30.5
4.8
29.5
44.7
25.7
14.3
63.8
89.0
36.2
—
14.3
* Molar ratio (relative to the COOH groups of the polymeric PAI chain).
** Duration of esterification.
ether of the azo dye with respect to the content of carboxy
groups in the polymer or more than 3% of the catalyst
relative to the PAI weight does not increase substantially
the degree of esterification. In this case, the reaction temꢀ
perature and its duration are the determining parameters
(Table 1). The use of a twofold excess of a glycidyl ether
(3 or 4) with respect to the carboxylꢀcontaining PAI,
DMBA as a catalyst, and 60 °C were the optimum condiꢀ
tions for PAI modification (see Table 1). The modificaꢀ
tion of PAI is depicted in Scheme 4.
According to the data from UV spectroscopy, the specꢀ
tra of glycidyl ethers of azo dyes 3 and 4 have absorption
maxima at λmax = 370 and 420 nm, respectively (Fig. 1).
No considerable shift of the absorption maximum was
observed after the reaction of compound 3 with the polyꢀ
mer (Fig. 2), which indicates the complete retention of
the chromophore structure after its introduction into the
side chain of the polymer.
All further mechanical, thermochemical, and thermoꢀ
gravimetric studies were carried out for PAI samples modiꢀ
fied with glycidyl ether 3 (PAIꢀ1).
Thermal stability of polymers with side chromophoric
groups is one of the most important characteristics.
Thermogravimetric data make it possible to estimate
boundaries of thermal stability of the synthesized materiꢀ
als. The TGA data for the prepared dyes and PAIꢀ1 with a
modification degree of 50% are given in Table 2.
As follows from the data in Table 2, the starting PAI
possesses rather high thermal stability typical of this class
of polymers: the temperature of the onset of its thermal
destruction is above 300 °C. Azo dye 1 is noticeably infeꢀ
rior to PAI in its thermal stability. At the same time, the
thermal stability of PAIꢀ1 is similar to that of the starting
polymer and even somewhat greater. Most likely, the polyꢀ
meric environment of the dye introduced into PAI enꢀ
hances its thermal stability.
Scheme 4

1484
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 6, June, 2005
Goikhman et al.
A
Table 3. Mechanical characteristics (Young´s modulus (E), ultiꢀ
mate tensile strength (σ ), and ultimate tensile strain (ε )) and
u
u
glass transition temperatures (Tg) of the PAIꢀ1 films at different
contents of chromophoric groups (α)
0.4
1
α (%)
E/GPa
σ /MPa
ε
u (%)
Tg/°C
u
0.3
0.2
0.1
0
2.80
3.06
2.78
3.32
2.77
75
86
74
87
74
38
45
40
77
51
116
123
123
123
124
15
30
50
90
2
300
400
500
λ/nm
properties of the polymers would allow one to determine
the temperature range of exploitation of articles based on
them and to choose optimum conditions for orientation
of side chromophoric groups in an electric field (the soꢀ
called poling), which occurs at temperatures close to the
glass transition temperature of the polymer. The main
mechanical characteristics and glass transition temperaꢀ
tures (Tg) of the starting and modified polymers with difꢀ
ferent degrees of esterification (α) are given in Table 3.
As can be seen from the data in Table 3, films of all the
synthesized polymers have high mechanical strength. High
values of Young´s modulus of the polymers indicate strong
intermolecular interactions in them. It is noteworthy that
the character of plots of the mechanical characteristics vs.
degree of modification of the starting polymer is extreme:
the maximum values of all parameters are observed for the
films of esterified PAI with α = 50%. This suggests that
the side chains can play an ordering role in polymer strucꢀ
ture formation when their concentration is not too high
and creates no hindrance for mutual packing.
Fig. 1. UV spectra of chromophores 3 (1) and 4 (2).
A
1.0
0.8
0.6
0.4
2
1
0.2
300
350
400
450
λ/nm
Fig. 2. UV spectra of the original PAI (1) and PAIꢀ1 with a
degree of modification of 30% (2).
The thermomechanical curves of the films of all the
modified polymers demonstrate two pronounced transiꢀ
tions: at low temperature (120—125 °C), which reflects
the process of material softening, and at high temperature
(225—240 °C). The nature of the latter is being refined.
However, we can assume at present that this transition
indicates that the material contains ordered structures.
The data of thermomechanical measurements were conꢀ
firmed by the results of optical dilatometry. On the whole,
the data from thermomechanics and dilatometry suggest a
complex character of thermorelaxation processes in the
materials under study. Finally, a comparison of the reꢀ
sults of thermomechanical studies and TGA (see Tables 2
and 3) suggests that the thermal characteristics of the
materials favor the orientation of the side groups near the
glass transition temperature: the segmental mobility is
disinhibited at comparatively low temperatures, which lie
much lower than the range of the onset of thermoꢀ
destruction of the material.
Table 2. Thermal stability of the synthesized chromophores and
polymers
Comꢀ
pound
τ
τ
τ
10
1
5
°C
1
258
333
341
290
358
370
297
377
397
PAI
PAIꢀ1
Note. τ , τ , and τ are the temperatures at which the mass
1
5
10
losses of the sample upon heating were 1, 5, and 10%, respecꢀ
tively.
Studies of the mechanical and thermomechanical
properties of the synthesized polymers are required to
make final conclusion about a possibility of their usage.
The polymers used in optical devices should possess rather
high strength in addition to necessary optical characterisꢀ
tics, because these materials can undergo mechanical loads
during exploitation. Studies of the thermomechanical
In the final stage of the work, we studied the nonlinear
optical properties of the modified polymers after they were
polarized in a corona discharge field. The intensity of

Polyamidoimides with pendent chromophores
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 6, June, 2005
1485
technique (UTStestsysteme, Germany) in a uniaxial extenꢀ
sion mode.
second harmonic generation in the polymeric films
was compared with that in a quartz crystal (d11
0.45 Pm V–1).8
=
Thermogravimetric analyses of the chromophores and polyꢀ
mers were carried out on a laboratory thermobalance, conꢀ
structed on the basis of ADBꢀ200 laboratory analytical balꢀ
ances, in a selfꢀgenerated atmosphere with a rate of temperature
increase of 5 deg min–1. The sample mass was 50 mg. The temꢀ
peratures at which mass losses of the sample during heating
reached 1, 5, and 10% (τ , τ , and τ10, respectively) were deterꢀ
The nonlinear optical coefficients (deff) for the polyꢀ
mer modified with chromophore 3 are 2.7, 3.3, 4.7, and
7.6 Pm V–1 at the degrees of substitution of 15, 30, 50,
and 90%, respectively, and remain almost unchanged for
one month. The deff value for PAIꢀ2 with a degree of
modification of 20% was 2.0 Pm V–1, i.e., somewhat
lower than that for PAIꢀ1 with the same degree of modifiꢀ
cation. At the same time, the PM3 quantumꢀchemical
calculation predicts9 a 1.6ꢀfold higher molecular square
nonlinearity for chromophore 4 than that for 3 (β =
27•10–30 and 16.6•10–30 esu, respectively). It can be asꢀ
sumed that considerably higher orientation of the side
chromophoric groups can be achieved in corona for the
films of the polymer modified with chromophore 3 than
that for the polymer modified with chromophore 4.
Thus, the method for esterification of polymers conꢀ
taining side carboxy groups with glycidyl ethers of dyes
was developed. The method provides wide potential for
introduction of chromophoric groups into the side chains
of polymers. The results obtained are significant for preꢀ
paring systems with nonlinear optical properties.
1
5
mined from the results of the tests.
Glass transition temperatures were determined by the
thermomechanical method on a UMIVꢀ3 instrument with the
load σ ≤ 0.5 MPa on the sample.
Studies on the nonlinear optical properties were carried out
with samples of films with the thickness from 1.5 to 2.5 µm
prepared by centrifugation on cover glass plates 180 µm thick.
The samples were dried in vacuo for 2 days at 50 °C. The samples
were polarized in a corona discharge field. The distance from
the tungsten needle electrode to the sample was 1 cm and the
corona discharge voltage was 6 kV. The current through the
sample did not exceed 2 µA.
The nonlinear optical properties of samples were studied by
recording the intensity of second harmonic generation under
YAGꢀNd3+ laser pulse irradiation. The wavelength of the inciꢀ
dent radiation was 1.06 µm, and the pulse duration was 15 ns.
The efficiency of second harmonic generation was characterized
by the nonlinear optical coefficient of the film (deff).
N,N´ꢀHexamethylenedi(trimellitimidic acid). A solution of
trimellitic anhydride (49 g, 0.25 mol) in DMF (250 mL) with a
temperature not exceeding 10 °C was added with stirring to a
solution of 1,6ꢀhexamethylenediamine (14.8 g, 0.13 mol) in
DMF (120 mL) at 0 °C under argon. The mixture was stirred for
6 h at ∼20 °C, then freshly distilled Ac2O (30.5 mL, 0.32 mol)
and pyridine (7.5 mL, 0.093 mol) were added, and the resulting
solution was refluxed for 6 h. This resulted in a yellow solution,
which yielded white crystals of N,N´ꢀhexamethylenedi(triꢀ
mellitimidic acid) after ∼12 h at ∼20 °C. The precipitate was
filtered off, washed with acetone and ether, and dried. The yield
was 33.5 g (56.5%).
N,N´ꢀHexamethylenedi(trimellitimidic acid) dichloride. The
acid obtained (15 g, 0.032 mol) was refluxed for 10 h with SOCl2
(120 mL). After cooling to ∼20 °C, a white precipitate that
formed was filtered, thoroughly pressed on a filter, and dried in
air for 40 min. The yield of the target acid chloride was 8.5 g
(52%), m.p. 169—171 °C. Found (%): C, 57.52; H, 3.61; N, 5.58;
O, 19.12. C24H18Cl2N2O6. Calculated (%): C, 57.49; H, 3.59;
N, 5.59; O, 19.16.
Experimental
NꢀMethylpyrrolidone and DMF were dried with CaH2
and distilled in vacuo. Thionyl chloride and acetic anhydride
were distilled, collecting fractions with b.p. 75.5—77 and
139—140 °C, respectively. Pyridine was dried with granulated
KOH and distilled, collecting a fraction with b.p. 114—115 °C.
3,5ꢀDiaminobenzoic acid, CPC, and DMBA were purified
using a known procedure.10 Katamine (AB trade mark,
Me(CH2)nN+Me2BnCl–; n = 8—16) was used as a 52% aqueous
solution without additional purification. 2ꢀAminobenzothiazole
(97% purity) and trimellitic anhydride (99% purity, Aldrich)
were used as received. 1,6ꢀHexamethylenediamine was distilled
in vacuo (m.p. 43 °C).
The degree of substitution of carboxy groups was determined
by potentiometric titration of solutions of precipitated samples
of the esterified polymers in DMF with a 0.08 M aqueous soluꢀ
tion of KOH.
Films for physical studies were prepared from solutions of
the respective polymers by casting onto glass plates using a temꢀ
plate followed by vacuum drying in a stepwise temperature—time
mode (final temperature 100 °C) to a constant mass. The film
thickness was 30—40 µm.
UV spectra of films were measured on a Specord UVꢀVIS
instrument in the 200—500 nm interval using a commercial
system (Casper Instr. Co) with a 350ꢀW mercury lamp as a
source. 1H NMR spectra of 1% solutions were obtained on a
Вruker ACꢀ200 spectrometer (200 MHz) with Me4Si as an inꢀ
ternal standard.
Synthesis of PAI (cf. Ref. 6). N,N´ꢀHexamethylenedi(triꢀ
mellitimidic acid) dichloride (4.4485 g, 0.00887 mol) was added
with stirring to a solution of 3,5ꢀdiaminobenzoic acid (1.31 g,
0.0086 mol) in NMP (28.5 mL) at –10 °C. The mixture was
stirred for 30 min, after which cooling was discontinued. After
20 min, propylene oxide (1 mL) was added, and stirring was
continued for 4 h at ∼20 °C. If the solution was very viscous, it
was diluted with NMP to a 10% concentration. The resulting
solution of the polymer was poured as a thin stream into 1 L of
water with permanent stirring. Polymer fibers were filtered off,
washed with acetone, and dried in vacuo for 24 h at 50 °C. The
yield was 90%. Found (%): C, 64.14; H, 4.14; N, 9.65; O, 22.07.
C31H24N4O8. Calculated (%): C, 64.12; H, 4.16; N, 9.61;
O, 22.11. 1H NMR (DMSOꢀd6), δ: 1.35 (s, 4 H, H(3´), H(4´));
Mechanical tests of the films, where Young´s modulus (Е),
ultimate tensile strength (σ ), and ultimate tensile strain (ε )
u
u
were determined, were carried out with a UTS 10 universal

1486
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 6, June, 2005
Goikhman et al.
1.62 (s, 4 H, H(2´), H(5´)); 3.60 (m, 4 H, H(1´), H(6´)); 7.95
(d, 2 H, H(5), J = 7.9 Hz); 8.16 (s, 2 H, H(3)); 8.42 (d, 2 H,
H(6), J = 7.9 Hz); 8.52 (s, 2 H, H(2″)); 8.71 (s, 1 H, H(4″));
10.73 (s, 2 H, NH).
4ꢀ(4ꢀNitrophenylazo)phenol (1) and 4ꢀ(6ꢀnitrobenzoꢀ
thiazolꢀ2ꢀylazo)phenol (2) were synthesized according to a
known procedure.11
6.99 (d, 2 H, H(2), H(6), J = 8.4 Hz); 7.88 (d, 2 H, H(3), H(5),
J = 8.4 Hz); 8.01 (d, 2 H, H(2´), H(6´), J = 9.3 Hz); 8.37 (d,
2 H, H(3´), H(5´), J = 9.3 Hz); 10.68 (s, 1 H, OH).
4ꢀ(6ꢀNitrobenzothiazolꢀ2ꢀylazo)phenol (2). Glacial AcOH
(35 mL) and a solution of 2ꢀaminobenzothiazole (5.1 g,
0.026 mol) in glacial AcOH (150 mL) were added to a solution
of NaNO2 (1.98 g, 0.028 mol) in concentrated H2SO4 (30 mL)
at 10—12 °C. The suspension was stirred for 20 min at 12 °C and
poured onto crashed ice (150 g). The resulting mixture was
poured with stirring into a solution of phenol (2.45 g, 0.026 mol)
in 50% AcOH (50 mL) cooled to 0—5 °C. After 1 h, a red
precipitate was filtered off, washed with water to neutral pH,
and recrystallized from ethanol. The yield was 2.92 g (50%),
m.p. 274 °C. Found (%): C, 52.04; H, 2.62; N, 18.69; O, 15.93;
S, 10.73. C12H8N4O3S. Calculated (%): C, 52.00; H, 2.69;
N, 18.66; O, 15.98; S, 10.68. 1H NMR (DMSOꢀd6), δ: 6.96 (d,
2 H, H(2), H(6), J = 8.6 Hz); 7.94 (d, 2 H, H(3), H(5), J =
8.6 Hz); 8.14—8.46 (m, 2 H, H(4´), H(5´)); 9.07 (s, 1 H, H(7´));
11.17 (s, 1 H, OH).
4ꢀ(4ꢀNitrophenylazo)phenol (1). A mixture of pꢀnitroaniline
(20 g, 0.15 mol), concentrated HCl (51 mL), and water (87 mL)
was heated with stirring to 70 °C, the solution was cooled to
∼20 °C, more water (145 mL) was added, and the resulting
mixture was cooled to –8 °C. A solution of NaNO2 (12.2 g,
0.177 mol) in water (28.5 mL) was cooled to 5 °C and poured
into a suspension of pꢀnitroaniline. Diazonium chloride is formed
with heat evolution and temperature should not exceed 5 °C.
The suspension gradually transformed into a solution. After
30 min, an emulsion of phenol was poured to this solution of diaꢀ
zonium chloride, maintaining temperature not higher than 0 °C
(the emulsion was prepared as follows: phenol (14.5 g, 0.154 mol)
was dissolved on heating in water (145 mL), and the mixture was
cooled to ∼20 °C). Then, a solution of Na2CO3 (54.3 g, 0.51 mol)
in water (220 mL) was added to the reaction mixture. The reꢀ
sulting suspension was stirred for 2 h, maintaining the temperaꢀ
ture at a level not higher than 10 °C. Then the suspension was
diluted with equal volume of water, heated to 50—60 °C with
continuous stirring, cooled to 40 °C, and acidified with hydroꢀ
chloric acid to pH 5—6. The resulting brown precipitate was
filtered off, washed with large amount of water, and thoroughly
pressed. The product was recrystallized from glacial AcOH. The
yield was 29.5 g (84%), m.p. 213—214 °C. Found (%): C, 59.45;
H, 3.67; N, 17.31; O, 19.57. C12H9N3O3. Calculated (%):
C, 59.26; H, 3.73; N, 17.28; O, 19.73. 1H NMR (DMSOꢀd6), δ:
Glycidyl ethers of azo dyes were synthesized according to a
described procedure.12
Glycidyl ether of 4ꢀ(4ꢀnitrophenylazo)phenol (3). Sodium carꢀ
bonate (3.22 g, 0.03 mol) and a 52% solution of katamine AB
(32.4 mL, 0.04 mol) were added to a mixture of 4ꢀ(4ꢀnitroꢀ
phenylazo)phenol (1) (29.5 g, 0.12 mol) and epichlorohydrin
(38 mL) at 55 °C followed by a 50% aqueous solution of NaOH
(10.7 mL) with vigorous stirring at a temperature not exceeding
60 °C. The mixture was stirred for additional 3 h at 55—60 °C,
cooled to ∼20 °C, and poured into a solution of NaOH (4.85 g)
and borax (23 g) in water (1210 mL). The precipitate that formed
was filtered off, washed with water, dried, and purified by chroꢀ
matography on a column with Al2O3 (eluent acetone). The yield

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