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Synthesis and Characterization of Highly Soluble Uorescent Main Chain Copolyimides Containing Perylene Units
Synthesis and Characterization of Highly Soluble Uorescent Main Chain Copolyimides Containing Perylene Units
Synthesis and Characterization of Highly Soluble Uorescent Main Chain Copolyimides Containing Perylene Units
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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 colorful liquid crystal display [6]. But most of the studied
perylene imides are insoluble and therefore the prepa-
3,4,9,10-Perylene tetracarboxylic dianhydride is a ration of thin films is carried out by vapor deposition
commercial monomer [1] and its derivates perylene imi- method or blending low molecular weight perylene imi-
des represent a class of n-type semiconductors exhibiting des with polymers to prepare smooth films possessing the
relatively high electron affinity among large-band-gap inherent problem of phase separation.
materials. At the same time they are well known chro- In order to expend the field of organic electrooptic
mophores combining high quantum yields of photolu- devices, which utilize polymers as active materials, it is
minescence with excellent photochemical and thermal worthwhile to design soluble and film-forming polymers
stability. These low molecular weight perylene imides are with enhanced electron transport property and fluores-
successfully used in optical switching [2], electrolumi- cence behave. Therefore the synthesis of soluble polyi-
nescent devices [3,4], solar energy conversion [5] and 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
*
Corresponding author. Tel.: +86-21-54742665; fax: +86-21- have much better properties than their low molecular
54741297. weight derivates. Now there are two approaches to
E-mail address: dyyan@mail.sjtu.edu.cn (D. Yan). 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
g (1.0 mmol) MBTBA, 15 ml p-chlorophenol and 15 vigorously stirring methanol. The pink fiber like pre-
drops quinoline. The mixture was stirred and heated to cipitated copolyimide was collected by filtration, washed
140 °C in 2 h and kept at 190 °C for 10 h. After cooling with methanol and dried under vacuum at 100 °C. For
to the room temperature, 0.2169 g (0.995 mmol) PMDA further purification the polymer was dissolved in 30 ml
was added into and the mixture was heated again at 100 CHCl3 , reprecipitated in methanol, dried under vacuum
°C for 10 h and 200 °C for 20 h. Then the highly viscous at 100 °C. Reprecipitation was repeated twice.
1
polymer solution was cooled to room temperature, di- H NMR [300 MHz, DCCl3 ]: d ðppmÞ ¼ 8:48–8:55
luted with 20 ml CHCl3 and was poured into 300 ml (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.
Scheme 2.
1102 W. Huang et al. / European Polymer Journal 39 (2003) 1099–1104
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 All copolyimides can emit strong green-yellow fluo-
showed in Fig. 2. All of them were stable up to 400 °C as rescence in chloroform solution with an emission max-
expectedly and exhibited high glass transition tempera- imum wavelength around 536–560 nm and the intensity
tures (Tg ), ranged from 340 to 360 °C, measured by depends strongly on the amount of the incorporated
DSC. Thus, the pendent tert-butyl groups attached to PTDA moiety in copolymer chains at the same copoly-
the backbone can considerably improve the solubility of mer concentration. Comparing with the emission spectra
the copolyimides without detriment to their thermal of monomer PTDA, the red shift 10 nm was observed
stabilities. Thus these polymers fulfill the requirements (Fig. 3). This confirmed again that PTDA was poly-
of high temperature stability and high Tg value for many merized into the copolyimides backbone. But the pho-
electrooptical thin layer devices. toluminescence spectra of the copolyimides in solid films
The UV absorption spectra of the monomer PTDA changed heavily comparing with their fluorescence
and copolyimides in CHCl3 solution are shown in Fig. 1. spectra in solution. When the percent of PTDA moiety
All copolyimides absorb at the maximum wavelength in these copolyimides was low (lower than 0.53 mol%),
526 nm and the monomer PTDA absorb at the maxi- the fine structure of emission peak was found. The first
mum wavelength 514 nm. The red shift (about 12 nm) maximum peak appeared around 538 nm and second
occurred between the copolymers and the monomer. around 576 nm. At the same time the emission peak
This may be caused by the chemical structure change became wider (500–700 nm) than those in chloroform
from perylene tetracarboxylic dianhydride to perylene solution. With the increasing of PTDA moiety con-
imide. The absorption intensity of PTDA is much more taining in polymer, the 538 nm emission peak and the
weak than that of the copolyimides because the mono- 576 nm emission peak became weak and the new wide
mer PTDA is very poor soluble in CHCl3 , but the ab- emission peak was formed around 625 nm (Fig. 4). This
sorption peak types of PTDA and copolyimides are may be caused by the copolyimide chains aggregation in
simliar. The absorption intensity of these copolyimides solid film state to form some electrotransforming com-
improves with the chromophore containing increasing in plex. On the other hand the emission intensity decreased
the polymers at the same polymers concentration in with the increasing of PTDA moiety containing in
CHCl3 solution.
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
Acknowledgements
50000
2
We like to thank Prof. Xiaoyuan Hou, Dr. Gaoyu
40000 3 Zhong and Ms Yi Liu (Surface Physics National labo-
ratory, National Key Laboratory, Fu Dan University)
30000 1 for measuring the fluorescence spectra of the copolyi-
mides in solid state film.
20000
4
10000 5
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