European Polymer Journal 45 (2009) 31083115

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European Polymer Journal

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Synthesis of soluble and thermally stable polyimide from new diamine

bearing N-[4-(9H-carbazol-9-yl)phenyl] formamide pendent group
Mousa Ghaemy *, Raouf Alizadeh, Hossein Behmadi
Faculty of Chemistry, University of Mazandaran, Babolsar 47416-1467, Iran

a r t i c l e

i n f o

Article history:
Received 23 May 2009
Received in revised form 9 August 2009
Accepted 13 August 2009
Available online 20 August 2009
Keywords:
Polyimide
Polycondensation
Thermal properties
Carbazole

a b s t r a c t
A new aromatic diamine monomer, N-(4-(9H-carbazol-9-yl)phenyl)-3,5-diaminobenzamide, was successfully prepared in four steps using carbazole as starting material and
polymerized with three aromatic tetracaboxylic acid dianhydrides via the conventional
two-stage synthesis including the polyaddition and chemical cyclodehydration to produce
a series of the aromatic polyimides. The polyimides were characterized by FT-IR, 1H NMR,
and 13C NMR spectroscopy, differential scanning calorimetric (DSC) and thermo gravimetric analysis (TGA) analysis. The polyimides with inherent viscosities in the range of 0.38
0.46 dL/g showed excellent solubility in various solvents such as N-methyl-2-pyrrolidinone
(NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), pyridine and
dioxane. DSC showed the glass transition temperatures (Tg) in the range of 277288 C.
TGA showed that all polymers were stable, with 10% weights loss recorded above 524 C
in air atmosphere. Preliminary tests on lms of the polyimides indicate that the materials
are brittle.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Aromatic polyimides are well accepted as high-performance polymers because of their good thermal and chemical stability, excellent mechanical properties, and high
glass transition temperatures [1,2], and are widely used
in various elds including aerospace and electronic industries. However, these polymers are difcult to process due
to their high glass transition temperatures (Tg), or high
melting temperatures (Tm), and limited solubility in organic solvents [3,4]. Considerable efforts have been made to
improve the solubility and/or melting processability of
polyimides while maintaining their positive properties
[57]. Therefore, some signicant synthetic efforts, in the
area of high-performance polymers have been focused on
improving their processability and solubility through design and synthesis of new monomers. A variety of structural modications to the polyimide backbone, such as
insertion of exible linkage on the main chain [8,9] and
* Corresponding author. Tel./fax: +98 112 5342350.
E-mail address: ghaemy@umz.ac.ir (M. Ghaemy).
0014-3057/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2009.08.012

utilization of noncoplanar or asymmetric monomers

[9,10], incorporation of pendent groups in the polymer
backbone [5,1014], can be employed to modify the polymer properties, either by lowering the inter-chain interactions or by reducing the stiffness of the polymer chain.
Depending on the type and amount of structural modications, the melting temperatures can be lowered and the
solubility improved, resulting in processable materials.
The objective for selection of heterocyclic rings in the
main chain or as pendent group of the synthetic polymer
is to impart certain properties to the polymer. Among different heterocyclic rings, the advantage of using a carbazole nucleus is based on its high thermal stability and
photoconductive property derived from the conjugated
aromatic rings [1519]. Also, carbazole and its many derivatives can be functionalized and thus have been covalently
incorporated into polymeric systems, both in main chain as
building blocks and in side chains as pendent groups.
In continuation of our previous study [11] in the search
for novel polyimides with improved processability and solubility, we herein report the synthesis of a new diamine
monomer, i.e. 3,5-diamino-N1-[4-(9H-carbazol-9-yl)phenyl]

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M. Ghaemy et al. / European Polymer Journal 45 (2009) 31083115

benzamide, containing N-[4-(9H-carbazol-9-yl)phenyl]

formamide pendent group. A series of all-aromatic polyimides were synthesized from the diamine with three commercial dianhydrides via a conventional two-stage process.
The characterizations of the diamine and related intermediates, as well as the resulting polyimide were carried
out by means of FT-IR, H NMR, C NMR, DSC, TGA and elemental analysis methods.
2. Experimental
2.1. Instrumentation and materials
All yields refer to isolated products. Melting points were
recorded on an electrothermal Stuart SMP3. The IR spectrometer used was Bruker Tensor 27. The IR spectra were
taken using KBr pellets. The 1H NMR spectra were recorded
on a 500 MHz Bruker Advance DRX instrument using
DMSO-d6 as solvent and tetramethyl silane as an internal
standard. Elemental analyses were run in a Flash EA 1112
series. Thermal gravimetric analysis (TGA) and differential
scanning calorimetry (DSC) analysis were performed using
TGA-50 and Mettler Toledo 822e in air atmosphere at
10 C/min, respectively. The inherent viscosity (ginh = Ln
[grel/C]) of the polymers were determined for the solutions
of 0.5 g/dl in NMP at 30 C using an Ubbelohde viscometer.
The solubility of the resulting polyimide was investigated
in different organic solvent by dissolving 10 mg of polymers in 1 mL of solvent at room temperature.
All the chemicals were purchased from Fluka. NMP was
distilled over CaH2 under reduced pressure. Reagent grade
aromatic dianhydrides such as Pyromellitic dianhydride
(PMDA), 3,30 ,4,40 -benzophenone tetracarboxylic dianhy-

dride (BPDA), and naphthalene-1,4,5,8-tetracarboxylic acid

dianhydride (NTAD) were dried under vacuum at 120 C
prior to use.

2.2. Monomer synthesis

2.2.1. N-(4-aminophenyl)-carbazole (II)
N-(4-aminophenyl)-carbazole (II) was prepared according to the procedure given in the literature [14], as shown
in Scheme 1, by the cesium uoride-mediated arylation of
carbazole with 4-uoronitrobenzene, followed by hydrazine Pd/C-catalyzed reduction of the intermediate compound, N-(4-nitrophenyl) carbazole (I). FT-IR/cm1: 3430,
3350 (NH2, stretching); 1622 (C@N, stretching); 1595
(C@C, stretching), 1392, 1229 (CN, stretching).

2.2.2. N-(4-(9H-carbazol-9-yl)phenyl)-3,5-dinitrobenzamide
(III)
N-(4-aminophenyl)carbazole (II), (5.16 g, 0.02 mol),
which was dissolved in 150 mL of dry acetone, and triethylamine (3 mL, 0.022 mol) were introduced into a 250-mL
ask equipped with magnetic stirrer bar, nitrogen gas inlet
tube and condenser. After the reaction solution was cooled
to 05 C, 3,5-dinitrobenzoyl chloride (4.61 g, 0.02 mol)
was added and the reaction mixture was maintained at
room temperature for 1 h, and then heated at reux for
4 h. The yellow precipitate was collected by ltration,
washed with water and acetone, and dried at 70 C under
vacuum overnight. The crude product was puried by
recrystallization in ethanol; yield 83% (7.59 g), mp 333
335 C.

NH2

NO2
NO2

H
N

Acetone
+

EtOH,

CsF

H2NNH2

NO2

O2N

C
3,5-dinitrobenzoyl chloride

(I)

NH
EtOH,

NMP

(II)
NH2

H 2N

NH

H2NNH2

(III)
Scheme 1. Synthesis of diamine.

(IV)

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M. Ghaemy et al. / European Polymer Journal 45 (2009) 31083115

NH2

H2N

O
Ar

Ar

PI C

n
C

O
C

NH
+ O
O

Ar

1) NMP, r. t.

O
PI C-a

NH

2) Ac2O, C5H5N

PI C-b

PI C-c

(DAC)
Scheme 2. Synthesis of polyimide.

FT-IR/cm1: 3410 (NH, stretching); 1677 (C@O, stretching); 1625 (C@N, stretching); 1593 (C@C, stretching);
1517, 1342 (NO2); 1408, 1228 (CN).
1
H NMR [DMSO-d6, d ppm]: 11.09 (s, 1H, NH); 9.22 (s,
2H); 9.02 (s, 1H); 8.25 (d, 2H, J = 7.75 Hz); 8.11 (d, 2H,
J = 8.6 Hz); 7.68 (d, 2H, J = 8.6 Hz); 7.477.40 (m, 4H); 7.3
(m, 2H).
2.2.3. N-(4-(9H-carbazol-9-yl)phenyl)-3,5diaminobenzamide (IV)
The dinitro compound (III) (4.52 g, 0.01 mol) and 10%
Pd/C (0.1 g) were suspended in 100 mL of ethanol in a
250-mL ask equipped with a condenser, magnetic stirrer
bar, and gas inlet tube. The suspension solution was heated

to reux, and 5 mL of hydrazine monohydrate was added

dropwise to the mixture over 1 h. After a further 6 h of reux, the resultant clear, darkened solution was ltered hot
to remove Pd/C, and the ltrate was then cooled to precipitate white crystals; yield 80% (3.14 g), mp 237238 C.
FT-IR/cm1: 3452, 3417, 3340, 3212 (NH, NH2, stretching); 1671 (C@O, stretching); 1626 (C@N, stretching);
1597 (C@C, stretching); 1365, 1236 (CN, stretching).
1
H NMR [DMSO-d6, d ppm]: 10.25 (s, 1H, NH); 8.25 (d,
2H); 8.07 (q, 2H); 7.56 (d, 2H); 7.42 (d, 2H); 7.37 (d, 2H);
7.29 (q, 2H); 6.37 (s, 2H, NH2); 6.05 (s, 2H, NH2).
13
C NMR [DMSO-d6, d ppm]: 168.4 (C@O), 150.08,
141.26, 139.94, 137.60, 132.36, 127.88, 127.05, 123.42,
122.11, 121.33, 120.72, 110.49, 103.22.

Fig. 1. FT-IR spectra of (III) and (IV).

M. Ghaemy et al. / European Polymer Journal 45 (2009) 31083115

2.3. Synthesis of polyimides

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3. Results and discussion

nucleophilic substitution reaction of 4-nitroourobenzene

with carbazole. N-(4-aminophenyl) carbazole (II) was prepared by hydrazine Pd/C-catalyzed reduction of the intermediate compound, N-(4-nitrophenyl) carbazole (I).
Monomer (IV) was prepared by condensation of N-(4-aminophenyl) carbazole (II) with 2,4-dinitrobenzoyl chloride
in dry acetone, followed by hydrazine Pd/C-catalyzed
reduction of the dinitro compound (III) in reuxing ethanol. FT-IR, 1H, and 13C NMR spectroscopic techniques were
used to identify the structures of the intermediate compound (III) and the diamine monomer (IV). The FT-IR spectra of dinitro compound (III) and diamine (IV) are
illustrated in Fig. 1. The nitro group of (III) gave two
characteristic bands at 1517 and 1342 cm1, which
disappeared after reduction. Diamine (IV) showed a typical
NH2 stretching absorption pair at 3452 and 3340 cm1.
The 1H NMR spectrum of dinitro (III) is shown in Fig. 2.
The assignment of each proton is also in the gure, and this
spectrum agrees well with the proposed structure. The
protons 2 and 3 of (III) resonated farthest downeld due
to the inductive effect of electron withdrawing NO2
groups.
The 1H NMR and 13C NMR of diamine (IV) are shown in
Fig. 3. The 1H NMR spectrum conrms that the nitro groups
have been completely converted into amine groups by the
high eld shift of the aromatic protons and by the signal at
4.98 ppm corresponding to the primary aromatic amino
protons. There are 14 resonance signals in the 13C NMR
spectrum of compound (IV) due to one carbonyl carbon
and 13 aromatic carbons.

3.1. Monomer synthesis and characterization

3.2. Polyimides synthesis and characterization

A new diamine containing N-phenyl carbazole pendent

group was prepared by the synthetic route outlined in
Scheme 1. Thus, the intermediate (I) was obtained by

The diamine monomer was polymerized with three aromatic tetracarboxylic dianhydrides as depicted in Scheme
2. The polymerization was carried out by reacting stoichi-

A typical procedure according to the literature [20] was

used for the preparation of polyimides. The diamine monomer (IV) (0.314 g, 0.8 mmol) was dissolved in 15 mL NMP.
After the diamine was dissolved completely, the aromatic
dianhydride (0.8 mmol), as shown in Scheme 2, was added
in one portion and an additional 5 mL of NMP. The solution
was stirred at room temperature under argon for 24 h to
obtain a viscous poly (amic-acid) precursor. To the viscous
solution were added 2 mL of acetic anhydride and 1 mL of
pyridine. The stirring was continued for 6 h at room temperature and 6 h at 60 C. The polymer was precipitated
into a 500 mL methanol and then ltered. The solid polymer was washed with hot water and methanol repeatedly,
and dried in a vacuum oven at 120 C for 24 h.
2.4. Preparation of the polyimide lm
Polyimide PI-a and PI-b were obtained as white powder
and PI-c as a red powder. A solution of polymer was made
by dissolving about 0.5 g of the polyimide sample in 10 mL
of DMF. The homogeneous solution was poured into a 9 cm
glass Petri dish, which was placed in a 70 C oven for 4 h to
remove most of the solvent; then the semidried lm was
further dried in vacuo at 130 C for another 2 h. The obtained lms were brittle.

Fig. 2. 1H NMR spectrum of (III).

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M. Ghaemy et al. / European Polymer Journal 45 (2009) 31083115

Fig. 3. (a) 1H NMR spectrum of (IV) and (b)

ometric amounts of diamine monomer (IV) with aromatic

dianhydrides in NMP. The ring-opening polyaddition was
carried out at room temperature for 24 h, which yielded
the poly (amic-acid) solution. The chemical imidization
with acetic anhydride and pyridine was employed to form
polyimides. The prepared polyimides that were obtained in
9095% yields had inherent viscosities (ginh) in the range of
0.380.46 dL/g. All the polymers were characterized using
FT-IR, 1H NMR and elemental analysis techniques and the

13

C NMR spectrum of (IV).

results are shown in Table 1. 1H NMR spectrum of PI-b is

shown in Fig. 4. The 1H NMR spectra of this polyimide
showed the expected multiplicity and integration values,
for example in this spectrum the amide proton of the pendent group was appeared at 10.5 and 10.7 ppm with 0.62
integration that related to one proton. The FT-IR spectra
of polyimides showed the absorption bands at 3420
(NH amide), 1770 (C@O asymmetric stretching), 1730
(C@O symmetric stretching), 1350 (CN stretching),

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M. Ghaemy et al. / European Polymer Journal 45 (2009) 31083115

Table 1
Reaction yields, FT-IR, and elemental analyses of polyimides.
Polyimide Yield (%) FT-IR m (cm1)

Elemental analysis
Calcd. (%)
C

Found (%)
N

PI-a

94

3430, 3070, 2924, 1777, 1723, 1667, 1595, 1515, 1348, 1228, 1108, 831, 752, 723 73.17 3.13 9.75 73.5

PI-b

91

3425, 3058, 1777, 1734, 1668, 1594, 1451, 1358, 1245, 1092, 987, 748, 714

74.11 3.23 8.23 74.57 3.33 8.48

PI-c

90

3420, 3120, 1773, 1730, 1670, 1594, 1507, 1407, 1301, 1236, 1150, 1122, 1024,
939, 809, 734

75.00 3.20 8.97 74.76 3.33 9.06

720 (C@O bending) cm1 corresponding to the characteristic imide bands. The FT-IR spectra of polyimides are
shown in Fig. 5.
3.3. Polyimides solubility
The solubility of the resulting polyimides were investigated in different organic solvents by dissolving 10 mg of
polymers in 1 mL of solvent at room temperature or upon
heating, and the results are shown in Table 2. It can be seen
that almost all the polyimides exhibited good solubility in
common organic solvents such as NMP, DMAc, DMF, and
DMSO even at room temperature. The enhanced solubility
of the resulting polyimides is attributed not only to the
bulkiness of the pendent N-phenyl carbazole groups but
also to the unsymmetrical structure coming from the diamine monomer. In addition, the solubility varies depending upon the dianhydride used. A comparison of the
solubility of PI-b polymer with the other two polymers
showed that this polymer has better solubility in NMP,
DMAc, DMF, THF and 1,4-dioxane at room temperature.
The carbonyl bridge unit into the structure of PI-b improves solubility of this polyimide in comparison with PIa and PI-c.

2.98 9.86

3.4. Thermal properties of polyimides

DSC and TGA methods were applied to evaluate the
thermal properties of the polyimides. DSC and TGA curves
of the polyimides are shown in Figs. 6 and 7, respectively.
Thermal analysis data from TGA and DSC tests of the polyimides are summarized in Table 3. The Tg values of the prepared polyimides were in the range of 277288 C, and no
melting endotherms were observed in the DSC traces.
These observations revealed the amorphous nature of the
polymer which could be attributed to their asymmetric
structural units and bulky pendent group, which decreased
the intra and inter-chain interaction, resulting in loose
polymer chain packaging and aggregates.
As we expected, the Tg values of these polyimides depended on the structure of the dianhydride component,
and decreased with increasing exibility of the polyimides
backbones based on the applied structure of dianhydride. It
is evident that the bridging carbonyl group between two
phenyl rings present in PI-b, facilitates bond rotation and
reduces Tg.
Thermal stability of polymers was evaluated by TGA in
air at a heating rate of 20 C/min. The temperature at 10%
weight loss was in the range of 527568 C. In addition,

Fig. 4. 1H NMR spectrum of PI-b.

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M. Ghaemy et al. / European Polymer Journal 45 (2009) 31083115

Fig. 5. FT-IR spectrum of polyimide.

Table 2
Solubility of synthesized polyimides.
Polyimide

PI-a
PI-b
PI-c

Solventa
NMP

DMAc

DMF

DMSO

Pyridine

THF

++
++
++

++
++
++

++
++
++

++
++
++

++
++
+


+


a
The symbols represent the following: ++, soluble at room temperature; +, partial soluble; , insoluble.

the residual weight retention at 600 C for the resulting

polyimides was in the range 5070%, implying that these
polyimides possess excellent thermal stability.
Comparison of the thermal behavior of polyimides
shows that PI-b has the lowest thermal stability, which is
attributed to the bridging carbonyl group between two
phenyl rings. The carbonyl bridging group between two
phenyl rings in the backbone of PI-b increased exibility
of polymer, therefore decreasing the thermal behavior.

Fig. 6. DSC thermograms of PIs.

M. Ghaemy et al. / European Polymer Journal 45 (2009) 31083115

3115

Fig. 7. TGA thermograms of PIs.

Table 3
Inherent viscosity and thermal properties of polyimides.
Polyimide

gin (dL/g)

Tg (C)

T10 (C)

Ch. Y (%)

PI-a
PI-b
PI-c

0.41
0.46
0.38

285 2
277 2
288 2

548 2
524 2
574 2

35 2
32 2
38 2

4. Conclusion
A series of novel polyimides were synthesized from different aromatic dianhydrides with the prepared diamine
monomer (IV) bearing the N-[4-(9H-carbazol-9-yl)phenyl]
formamide pendent group via a chemical imidization.
These polymers showed excellent solubility in conventional organic solvents. Introduction of bulky pendent
groups in polyimide backbone decreased close packing of
the polymer chains and inter-chain, thereby leading to
enhancements in solubility and decreasing crystallinity.
These polymers also have high glass transition temperatures and exhibited excellent thermal stability in air.
Preliminary tests on lms of the polyimides indicate that
the materials are brittle.
.
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