European Polymer Journal 39 (2003) 1099–1104

www.elsevier.com/locate/europolj

Synthesis and characterization of highly soluble

fluorescent main chain copolyimides containing perylene units
Wei Huang, Deyue Yan *, Qinghua Lu, Yue Huang
School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240,
PeopleÕs Republic of China
Received 11 September 2002; received in revised form 10 November 2002; accepted 13 November 2002

Abstract
A series of high molecular weight copolyimides containing various amount of perylene units in the main chain have
been synthesized. The polymers were characterized by FT–IR, NMR, UV/Vis, fluorescence spectroscopy, gel per-
meation chromatography, differential scanning calorimetry and thermogravimetric analysis measurements. They are
highly soluble in conventional solvents such as CHCl3 , THF, cyclohexanone etc. and form optically transparent films
by solution casting or spin coating. The incorporation of various amount of perylene units in the main chain allows the
control of the fluorescence intensity in solution and in solid thin films. The copolyimide containing 0.28 mol% perylene
units exhibits the highest solid-state fluorescence. The observed fluorescence intensities of the copolyimides in solid state
film decreased with the increasing amount of perylene units in the main chain when the mole ratio of perylene units
greater than 0.28 mol% indicating the aggregation of chromophores. The copolyimides are thermally stable up to 400
°C and exhibit glass transition temperatures in the range of 340–360 °C. The number average molecule weight ranges
from 1:72
104 to 1:25
105 and the molecule weight distribution mediated between 1.9 and 2.4.
Ó 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Fluorescence copolyimides; High solubility; Perylene units; Polycondensation; Tert-butyl groups

1. Introduction
3,4,9,10-Perylene tetracarboxylic dianhydride is a
commercial monomer [1] and its derivates perylene imi-
des represent a class of n-type semiconductors exhibiting
relatively high electron affinity among large-band-gap
materials. At the same time they are well known chro-
mophores combining high quantum yields of photolu-
minescence with excellent photochemical and thermal
stability. These low molecular weight perylene imides are
successfully used in optical switching [2], electrolumi-
nescent devices [3,4], solar energy conversion [5] and
*
Corresponding author. Tel.: +86-21-54742665; fax: +86-21-
54741297.
E-mail address: dyyan@mail.sjtu.edu.cn (D. Yan).
colorful liquid crystal display [6]. But most of the studied
perylene imides are insoluble and therefore the prepa-
ration of thin films is carried out by vapor deposition
method or blending low molecular weight perylene imi-
des with polymers to prepare smooth films possessing the
inherent problem of phase separation.
In order to expend the field of organic electrooptic
devices, which utilize polymers as active materials, it is
worthwhile to design soluble and film-forming polymers
with enhanced electron transport property and fluores-
cence behave. Therefore the synthesis of soluble polyi-
mides containing perylene moiety has generated much
more interesting in the field of polymer chemistry recent
years. Much of the stimulus for this increasing attention
comes from the expectation that these polymers should
have much better properties than their low molecular
weight derivates. Now there are two approaches to
synthesize soluble polyimides containing perylene units.

0014-3057/03/$ - see front matter Ó 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0014-3057(02)00360-9
1100 W. Huang et al. / European Polymer Journal 39 (2003) 1099–1104
One is to introduce long or bulky substituents at 1,6,7,12
‘‘bay positions’’ of the perylene core. For example,
Dotcheva et al. [7] reported some soluble polyimides
containing substituted perylene units in 1994. P} osch et al.
[8] synthesized some low molecular weight copolyimides
containing substituted perylene moiety and used as
electron transport moieties for electroluminescent de-
vices. Recently Thelakkat et al. [9] reported two series of
highly fluorescent main chain copolyimides containing
substituted perylene and quinoxaline units. On the other
hand, some soluble polyimides containing unsubstituted
perylene units have been reported too. For example,
Ghassemi and Hay [10] reported the red pigmentary
polyimides made from N; N 0 -diamino-3,4,9,10-perylene
tetracarboxylic acid bisimide. Icil and Icli [11] synthe-
sized a new photostable polymer based on perylene-
3,4,9,10-tetracarboxylic acid-bis-(N ; N 0 -dodecylpolyimide).
Wang and coworkers [12–14] prepared some novel
perylene containing polyimides and investigated their
xerographic electrical properties, voltage dependent flu-
orescence etc. But most of them only dissolved in
strong polar solvents such as m-cresol or concentrated
H2 SO4 .
Recently, the authors [15,16] of this work developed a
series of highly soluble polyimides consist of 4,40 -meth-
ylene-bis-(2-tert-butylaniline) and various aromatic
dianhydrides. Simultaneously the solubility of the com-
mercial low molecular weight perylene imides N; N 0 -bis-
(2,5-di-tert-butylphenyl)-3,4,9,10-perylene dicarboxyimide
(Adrich) [17], which can be used in solar energy con-
version collector, is improved greatly on account of the
tert-butyl groups belong to the aromatic amine. In this
work we reported the synthesis and characterization of a
series of soluble aromatic copolyimides from 3,4,9,
10-perylene tetracarboxylic dianhydride, pyromellitic
dianhydride and the aromatic diamine containing tert-
butyl pendent groups (4,40 -methylene-bis-(2-tert-buty-
laniline)) and investigated their solubility, thermal
stability, photoluminescence in solution and solid state
film.
2. Experimental
2.1. Materials
Pyromellitic dianhydride (PMDA) (Wujing Chemical
Co.) was recrystallized from acetic anhydride; 3,4,9,10-
perylene tetracarboxylic dianhydride (PTDA) (Aldrich)
was purified according to Ref. [12]; 2-tert-butyl-
aniline (Aldrich); 4,40 -methylene-bis-(2-tert-butylaniline)
(MBTBA) was synthesized in our laboratory [17];
p-chlorophenol (PCP), quinoline, methanol and other
solvents was purchased from domestic chemical market
and used without further purification.
2.2. Characterization
FT/IR spectra were recorded on a PE FT/IR spec-
trometer; UV/Vis spectra were recorded on a PE
Lambda 20 UV/Vis spectrometer; The fluorescent spec-
tra of copolyimides in solution were recorded on PE
Luminescence Spectrometer LS50B; The photolumines-
cence spectra of the copolyimides in solid state film were
measured by He–Cd laser instrument; 1 H nuclear mag-
netic resonance (1 H NMR) measurements were carried
out on a 300 and 400 MHz Bruker NMR spectrometer
with CDCl3 as solvent. Thermogravimetric analysis
(TGA) was performed under nitrogen on a PE Pyris-7
thermal analyzer. The sample was heated on 20 °C/min
heating rate from 50 to 800 °C. Differential scanning
calorimetric (DSC) studies were conducted under ni-
trogen on PE Pyris-1 thermal analyzer. The sample was
heated on 20 °C/min heating rate from 50 to 380 °C. The
molecular weight was measured by PE Series 200 gel
permeation chromatography (GPC) analyzer and rela-
tive to polystyrene standards.
2.3. Synthesis of model compound
N ; N 0 -bis-(2-tert-butylaniline)-3,4,9,10-perylene tetra-
carboxylic diimide was synthesized from PTDA and 2-
tert-butylaniline according to the similar approach in
earlier literature [9] (Scheme 1) 2.2398 g (15 mmol) 2-
tert-butylaniline and 350 mg (1.92 mmol) anhydrous
zinc acetate were added into a solution of 1.00 g (2.5
mmol) PTDA in 20 ml quinoline. The mixture was
stirred at 220 °C for 16 h under nitrogen atmosphere.
After cooling to the room temperature the mixture was
added into 400 ml methnol/10% hydrochloride acid
(V=V ¼ 2:1) under the stirring. The solid precipitate was
filtered off and stirred in 100 ml cold sodium carbonate
solution (10%) for 2 h. Then the precipitate was filtered
again and washed with distilled water until the filtrate
was colorless and nonfluorescent. The solid was dried
under vacuum at 100 °C for 24 h to obtained 1.26 g dark
red powder.
1
H NMR [400 MHz, CDCl3 ]: d ðppmÞ ¼ 8:68–8:78
(8H, H in perylene unit), 7.68 (2H, arom.), 7.47 (2H,
arom.), 7.38 (2H, arom.), 7.25 (2H, arom.), 1.32–1.34
(18H, H in tert-butyl group).
FT/IR (KBr): t ðcm1 Þ ¼ 2963, 1703, 1665, 1592,
1577, 1505, 1489, 1356, 1346, 1251, 1198, 1150, 969, 852,
736, 689.
2.4. Polymer synthesis
The synthesis route of the copolyimides was shown in
Scheme 2. A typical synthesis procedure (for example
polymer 2) as follow: A 100 ml three necked flask
equipped with a nitrogen inlet and a mechanical stirring
was charged with 0.0020 g (0.005 mmol) PTDA, 0.3100
 W. Huang et al. / European Polymer Journal 39 (2003) 1099–1104
g (1.0 mmol) MBTBA, 15 ml p-chlorophenol and 15
drops quinoline. The mixture was stirred and heated to
140 °C in 2 h and kept at 190 °C for 10 h. After cooling
to the room temperature, 0.2169 g (0.995 mmol) PMDA
was added into and the mixture was heated again at 100
°C for 10 h and 200 °C for 20 h. Then the highly viscous
polymer solution was cooled to room temperature, di-
luted with 20 ml CHCl3 and was poured into 300 ml
Scheme 1.
Scheme 2.
1101
vigorously stirring methanol. The pink fiber like pre-
cipitated copolyimide was collected by filtration, washed
with methanol and dried under vacuum at 100 °C. For
further purification the polymer was dissolved in 30 ml
CHCl3 , reprecipitated in methanol, dried under vacuum
at 100 °C. Reprecipitation was repeated twice.
1
H NMR [300 MHz, DCCl3 ]: d ðppmÞ ¼ 8:48–8:55
(2H, arom.), 7.51 (2H, arom.), 7.26 (2H, arom.), 6.99
(2H, arom.), 4.14 (2H, H in methylene between two
arom. rings), 1:60–1:70 (H2 O), 1.33 (18H, H in tert-butyl
group), (no resonance signals from the perylene unit
were detected).
FT/IR (solution casting film): t ðcm1 Þ ¼ 3566, 3033,
2912, 2874, 1779, 1735, 1620, 1498, 1410, 1294, 1248,
1163, 1104, 1026, 980, 927, 876, 766, 728.
Other copolyimides are accessible by the same process
except that various amount of the solvent PCP was used
dependent on the amount of the monomer PTDA. The
color of resulting polymers varied from pink to light
violet depending on the perylene unit content. The 1 H
NMR and FT/IR data of them are similar as polymer 2.
3. Result and discussion
The synthetic route shown in Scheme 2 describes the
preparation of five different copolymers with varying
mol% perylene chromphore in main chain (from 0.075 to
1102 W. Huang et al. / European Polymer Journal 39 (2003) 1099–1104
2.50 mol% of weighed PTDA). The molar amount of
diamine MBTBA was kept to constant (50 mol%) and
the amounts of PTDA and PMDA were varied, keeping
the total amount of both dianhydrides equal to that of
diamine MBTBA. On account of the different reac-
tivity of the five-membered pyromellitic dianhydride
and the six-membered perylene dianhydride, a stepwise
polymerization was necessary to achieve a random in-
corporation of the comonomers. First, the diamine
MBTBA was allowed to react with the less reactive six-
membered dianhydride PTDA in the presence of quin-
oline at 190 °C, resulting in a mixture of unreacted
diamine MBTBA and amino-terminated incorporated
perylene species. In the second step, the more reactive
five-membered dianhydride PMDA was added when the
reaction mixture cool to the room temperature. Then the
reaction mixture was heated again and kept at 100 °C
for 10 h in order to obtain high molecular weight
poly(amic acid)s. In the final step these poly(amic acid)s
was kept at 200 °C for 20 h to imidize completely
by elimination of water via purging dry nitrogen. The
conventional approach of copolymerization by adding
all comonomers together at one time did not lead to the
series of copolymers with exact amounts of perylene
content and desired dilution effect. The completion im-
idization of these copolymers is indicated by absence of
O–H vibration band about 3000 cm1 , the C@O vibra-
tion band at 1670 cm1 of poly(amic acid) as well as the
C@O vibration band of the anhydride at 1850 cm1 .
Moreover two new bands at around 1778 and 1723 cm1
due to the imide C@O stretching vibration are observed
in the final polymers.
The general method for determining the composition
of a copolymer by NMR measurements could not be
used here due to the extremely small amount of incor-
porated perylene comonomers in polymers (less than 2.5
mol%). Therefore we adopted the extinction coefficient
(from UV/Vis spectroscopy measurements) correlation
of a model compound with these polymers to determine
the amount of incorporated perylene chromophores in
their main chain quantitatively. For this purpose,
we synthesized N; N 0 -bis-(2-tert-butylaniline)-3,4,9,10-
perylene tetracarboxylic diimide (Scheme 1) as model
compound because its similar substitution pattern as the
parent polymers and their UV/Vis spectra are nearly
same (Fig. 1). The optical density at the absorption
maximum (Amax ) was plotted vs. concentration (c in
mol l1 ) to obtained the absorption standard curve and
the extinction coefficient (emax in l mol1 cm1 ) from the
slope of the linear function, emax ¼ Amax =cl, where l is
the path length (cm). Here the extinction coefficient emax
for the model compound was 46,500 at 526 nm in
CHCl3 . Then a series of certain concentration dilute
solutions of these copolyimides were prepared and
measured by UV/Vis spectroscopy to get the optical
densities at the absorption maximum too. At last, ac-
0.04 4
model compound 3
PTDA
0.03
2
1
0.02 polymer
0
400 450 500 550 600
Fig. 1. UV-spectra of the monomer PTDA, model compound
and the copolyimide in CHCl3 solution (saturated solution of
PTDA in CH3 Cl; 0.43 mg (model compound)/50 ml CHCl3 ; 2.2
mg (polymer 5)/50 ml CHCl3 ).
cording to the absorption standard curve, the mole
fraction of incorporated perylene chromophore in the
polymers can be determined to be 0.08, 0.28, 0.53, 1.68,
2.84 mol% respectively. It can be seen that the stepwise
polycondensation adopted to prepare copolyimides re-
sults in the incorporation of perylene units in polymers
and in good agreement with the weighted molar amount
(Table 1).
The number average molecular weights (Mn ) of the
resulting copolyimides were ranging from 1:72
104 to
1:25
105 g/mol measured by GPC and the Mw =Mn were
between 1.9 and 2.4. With the increase of the PTDA
moiety in the copolyimide, the molecular weight de-
creased stepwise. This may be caused by the poor solu-
bility of PTDA in organic solvents and much more
solvent PCP should be used in order to make the solids
dissolved completely. The solid containing decreased in
the reaction mixture was harmful for synthesizing high
molecular weight polyimide.
The solubility of the copolyimides was measured at
concentration 0.05 g/ml at room temperature in various
solvents. It is well known that PMDA and PTDA are
the most rigid aromatic anhydrides so that the polyi-
mides or copolyimides containing PMDA and PTDA
are usually insoluble or poorly soluble in organic sol-
vents. It is interesting that the novel copolyimides pre-
pared in this research can be dissolved in common
organic solvents such as tetrahydrofuran, chloroform
and cyclohexanone at room temperature. The improve-
ment of the solubility can be attributed to the bulky tert-
butyl groups of the aromatic diamine that reduced the
interaction between copolyimide chains. These copoly-
imides can be processed easily in solution to form a
transparent, flexible and tough film when the PTDA
containing was lower than 2.84 mol%. Otherwise the
copolyimides cannot form films or their films are brittle.
 W. Huang et al. / European Polymer Journal 39 (2003) 1099–1104 1103

Table 1
Characterization of the copolyimides
Sample Y a (mol%) Y b (mol%) Mn Mw Mw =Mn Tg (°C)
4 5
Polymer 1 0.075 0.082 5:19
10 1:03
10 1.99 349.8
Polymer 2 0.250 0.281 1:25
105 2:37
105 1.90 346.0
Polymer 3 0.500 0.531 3:83
104 8:18
104 2.10 347.6
Polymer 4 1.500 1.682 2:53
104 6:18
104 2.41 353.4
Polymer 5 2.500 2.836 1:72
104 4:13
104 2.40 346.1
a
As weighed molar amount.
b
Determined by quantitative UV/Vis spectroscopy.

The typical TGA curves of these copolyimides are
showed in Fig. 2. All of them were stable up to 400 °C as
expectedly and exhibited high glass transition tempera-
tures (Tg ), ranged from 340 to 360 °C, measured by
DSC. Thus, the pendent tert-butyl groups attached to
the backbone can considerably improve the solubility of
the copolyimides without detriment to their thermal
stabilities. Thus these polymers fulfill the requirements
of high temperature stability and high Tg value for many
electrooptical thin layer devices.
The UV absorption spectra of the monomer PTDA
and copolyimides in CHCl3 solution are shown in Fig. 1.
All copolyimides absorb at the maximum wavelength
526 nm and the monomer PTDA absorb at the maxi-
mum wavelength 514 nm. The red shift (about 12 nm)
occurred between the copolymers and the monomer.
This may be caused by the chemical structure change
from perylene tetracarboxylic dianhydride to perylene
imide. The absorption intensity of PTDA is much more
weak than that of the copolyimides because the mono-
mer PTDA is very poor soluble in CHCl3 , but the ab-
sorption peak types of PTDA and copolyimides are
simliar. The absorption intensity of these copolyimides
improves with the chromophore containing increasing in
the polymers at the same polymers concentration in
CHCl3 solution.
All copolyimides can emit strong green-yellow fluo-
rescence in chloroform solution with an emission max-
imum wavelength around 536–560 nm and the intensity
depends strongly on the amount of the incorporated
PTDA moiety in copolymer chains at the same copoly-
mer concentration. Comparing with the emission spectra
of monomer PTDA, the red shift 10 nm was observed
(Fig. 3). This confirmed again that PTDA was poly-
merized into the copolyimides backbone. But the pho-
toluminescence spectra of the copolyimides in solid films
changed heavily comparing with their fluorescence
spectra in solution. When the percent of PTDA moiety
in these copolyimides was low (lower than 0.53 mol%),
the fine structure of emission peak was found. The first
maximum peak appeared around 538 nm and second
around 576 nm. At the same time the emission peak
became wider (500–700 nm) than those in chloroform
solution. With the increasing of PTDA moiety con-
taining in polymer, the 538 nm emission peak and the
576 nm emission peak became weak and the new wide
emission peak was formed around 625 nm (Fig. 4). This
may be caused by the copolyimide chains aggregation in
solid film state to form some electrotransforming com-
plex. On the other hand the emission intensity decreased
with the increasing of PTDA moiety containing in

1000
5
200
PTDA Polymer 800
1.0 4
150
600
0.8 3
100
PTDA incorporated in polymers 400
0.6 3
1 0.08 mol % 4 2
2 0.28 mol % 2 50 200
0.4 3 0.53 mol % 1
4 1.68 mol % 1
5 2.84 mol % 0 0
0.2 5 500 550 600 650

0.0
200 400 600 800 Fig. 3. Fluorescence spectra of the polyimide dissolved in
CH3 Cl (the concentration of copolyimide in solution was 2 mg/
200 ml CH3 Cl for polymer 1–4 and 1.5 mg/200 ml for polymer
Fig. 2. TGA curves of the copolyimides. 5, excitation wavelength was 526 nm).
1104 W. Huang et al. / European Polymer Journal 39 (2003) 1099–1104
50000
2
40000 3 Zhong and Ms Yi Liu (Surface Physics National labo-
30000 1 for measuring the fluorescence spectra of the copolyi-
20000
4
10000 5
0 [1] Stille DK. Condensation monomers. New York: Wiley-
500 600 700
Fig. 4. Photoluminescence spectra of the copolyimides in solid
film (thickness 20 lm, excited by the 441.6 nm He–Cd laser).
copolyimides could be explained by self-quenching
process occurred when aggregation of the dye molecules
in the solid state film. As a consequence, the copoly-
imide containing 0.28 mol% PTDA moiety displayed the
brightest yellow–green photoluminescence in the inves-
tigated series.
4. Conclusion
Overall a series of novel high molecular weight co-
polyimides containing tert-butyl and perylene units were
synthesized and characterized in this study. Those co-
polyimides are highly soluble in conventional solvents,
such as chloroform, tetrahydrofuran, cyclohexanone,
and easy to process to form films by solution casting or
spin coating. They are very stable until the temperature
was higher than 400 °C and exhibits high glass transition
temperature. All of them can emit yellow–green light
in solution and solid films. These highly fluorescent
copolymers are potential candidates for light-emitting
materials used in polymer electroluminescence device or
for other applications.
Acknowledgements
We like to thank Prof. Xiaoyuan Hou, Dr. Gaoyu
ratory, National Key Laboratory, Fu Dan University)
mides in solid state film.
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