High Performance Polymers

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One-Pot Polyimide Synthesis in Carboxylic Acid Medium

Alexander A Kuznetsov
High Performance Polymers 2000 12: 445
DOI: 10.1088/0954-0083/12/3/307
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High Perform. Polym. 12 (2000) 445460. Printed in the UK

PII: S0954-0083(00)14912-8

One-pot polyimide synthesis in carboxylic acid medium

Alexander A Kuznetsov
Institute of Synthetic Polymeric Materials, Russian Academy of Science, 70, Profsoyuznaya ul.,
Moscow, 117393, Russia
Received 23 June 2000
Abstract. The melts of aromatic carboxylic acids such as benzoic acid (BA) at 130160 C
were shown to be excellent media for the one-pot synthesis of high molecular weight, completely
cyclicized polyetherimides (PEIs) from the corresponding diamines and tetracarboxylic acid
dianhydrides. According to the data on the cyclodehydratation (CD) kinetics of oligomeric amic
acid model compounds, the rate of cyclicization of transient polyamic acids in BA at 140 C is very
high, and the polymer chain growth proceeds via the polyaddition of completely cyclicized PEI
oligomers with amino and anhydride end groups. Tetracarboxylic acids in BA at 140 C were shown
to react with aromatic diamines to obtain high molecular weight PEIs as well as the corresponding
dianhydrides. The effect of the total concentration of comonomers and the presence of an inert
diluent on the kinetics of the growth of the inherent viscosity in the polycyclocondensation of
diamines and dianhydrides is discussed from the point of view of the mechanism of the process. The
prospect of a novel synthetic approach in polyimide synthesis is discussed, including obtaining new
homopolyimides based on extremely-low-reactivity monomers; new statistical, regular, alternating
copolyimides and block copolyimides; two-component blends with one glass transition point, and
PEIs based on AB-type heteromonomers.

1. Introduction
Carboxylic acids are known to be catalysts in a large variety of organic reactions, including
the two reactions which are of great importance for polyimide chemistry, namely: (a) the
acylation of diamines with tetracarboxylic acid dianhydrides and (b) the cyclodehydratation
(CD) of o-carboxyamide (amic acid) moieties. In this connection, the idea of using carboxylic
acids in polyimide synthesis as a catalytic agent and the reaction medium simultaneously seems
to be attractive.
The kinetics and thermodynamics of the acylation of aromatic diamines with carboxylic
acid dianhydrides has been investigated in detail [15]. Acid catalysis in the acylation of
aromatic diamines was probably rst demonstrated by Litvinenko et al in the 1960s [6, 7]
and it was then studied in detail [810]. Thus, it was shown that addition of a small quantity
of chloroacetic acid (CAA) to a chloroform solution containing equimolar concentrations of
p-substituted anilines and phthalic anhydrides (PAs) results in the strong acceleration of the
reaction (see scheme 1) due to appearance of a catalytic channel [9].
In the absence of CAA, a clear autocatalytic behaviour occurs in CHCl3 and acectonitrile
(AcCN) because of the catalysis of the reaction by phenylphthalamic acid (PPA), the reaction
product, the rate constant of the direct reaction via the catalytic channel being an order
of magnitude greater than that via ordinary reaction [10]. In more basic solvents such as
dimethylacetamide (DMAA), the autocatalytic regime does not occur because of the strong
interaction of the amic acid with the solvent, and the overall acylation rate is not too large.
0954-0083/00/030445+16$30.00

2000 IOP Publishing Ltd

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445

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A A Kuznetsov

Scheme 1.

On the other hand, the strong interaction of the amic acids with the solvent leads to the
largest values of the acylation equilibrium constant (and connected with the latter, the degree
of polymerization of the polyamic acids) being achieved in just the amic solvents. A very
specic feature of the acid-catalysed acylation reaction in CHCl3 and AcCN is the extreme
dependence of the overall rate of the process versus the content of acid catalyst added, caused
by the protonation of amino groups with an excess of the catalyst. This fact probably explains
why high concentrations of carboxylic acid have not been used in one-pot polyimide synthesis.
Acid catalysis in the CD reaction of polyamic acid (PAA) was demonstrated rst in 1977
by Vinogradova et al [11] and Lavrov et al [12, 13]. In the absence of acid additives, clear
second order was found for the CD reaction of PAA by Lavrov et al [13] and Kim et al [14].
The self-catalysis of the CD reaction of model amic acids in concentrated solutions in amic
solvents was demonstrated by Kuznetsov et al [15], amic acid being the reagent and catalyst
simultaneously, and the solvent playing the role of co-catalyst.
Recently, we have discovered that the melts of aromatic carboxylic acids such as benzoic
acid (BA) at 130160 C can be used as the reaction media in catalytic one-pot syntheses
of high molecular weight completely cyclicized polyimides from corresponding diamines and
tetracarboxylic acid dianhydrides [1619]. This article is a development of the novel approach.
2. Experimental details
2.1. Starting materials
2,2-bis[(4-aminophenoxy)phenyl]propane (BAPP, technical grade product, Russia) was
puried by crystallization from isopropanol, Tm = 129 C. m-phenylenediamine (PDA,
Tm = 6466 C) and hexamethylenediamine (HMDA, Tm = 4445 C) were puried by
distillation in vacuo. 2,6-diaminopyridine (DAP, Aldrich) was puried by sublimation
in vacuo, Tm = 122 C. 4,4 -oxydianiline (ODA) (Russia) was puried by sublimation in vacuo,
Tm = 190 C. 4,4 -diaminodihenyl sulfone (Russia) was crystallized from isopropanol,
Tm = 175 C.
3,3 ,4,4 -biphenyltetracarboxylic acid (BPTA) was obtained by the dehydration of the
corresponding acid dihydrate (BPTA.2H2 O) at 200 C for 30 min. BPTA.2H2 O was
synthesized by Professor E L Vulah of the Research and Technical Design Institute of
Monomers (Tula, Russia) and it was kindly presented for our disposal. The 3,3 4,4 biphenyltetracarboxylic acid dianhydride (BPDA) was obtained by heating BPTA at 270 C for
2 h. BPDA displays only one peak in the differential scanning calorimetry (DSC) thermogram
at 300 C (literature data Tm = 286 C [20]). 4,4 -oxydiphthalic anhydride (technical
grade, Russia) was crystallized from acetic dianhydride and sublimated at 200 C in vacuo,
Tm = 221 C. 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and 4aminophenoxyphthalic acid (APPA) were synthesized by Professor M V Dorogov of the

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One-pot polyimide synthesis in carboxylic acid medium

447

Department of Organic Chemistry, State Yaroslavl Technical University (Russia) and used
as received; Tm = 188189 C (BPADA).
BA was puried by distillation under ambient pressure and an inert atmosphere,
Tm = 122 C; diphenylsulfone was crystallized from isopropanol, Tm = 126128 C; and
m-cresol was distilled under vacuum before use.
2.2. Synthesis of polyetherimide
The synthesis of polyetherimides (PEIs) from diamines and tetracarboxylic acid dianhydrides
in the melt of BA is described below by the example of PEI-2. 0.5825 g (1.42 mmol) of
BAPP, 0.4175 g (1.42 mmol) BPDA and 9.0 g of BA were loaded into a glass reaction vessel
equipped with a stirrer under a slow ow of argon. The reactor was placed into an oil bath at
140 C. After melting the BA a stirrer was turned on. The time to reach 140 C was less than
3 min. The reaction was carried out under an argon atmosphere for 1 h. At a denite time
after reaching 140 C, the probes were removed from the reaction medium. After cooling each
probe was treated with acetone to remove the BA; the polymer residue was dried and analysed
by Fourier-transform infrared (FTIR) spectroscopy and viscometry. The FTIR spectra were
obtained using a Nicollett FTIR, Impact 410 spectrometer; the samples for the FTIR were
made of CsI. The conversion of the CD reaction for PEI-2 was measured using the peaks at
1370 cm1 (CN vibration in the imide cycle) and 1500 cm1 (CC vibration in an aromatic
cycle; the internal standard). In the case of PEI-1 and other polymers based on BPADA, the
region of 1370 cm1 is not available because of its own absorption related to the isopropylidene
moiety. So, for the PEI of this group, the conversion of the CD reaction was estimated using
the intensity ratio of the peaks at 620 cm1 (imide cycle) and 690 cm1 (internal standard)
using a previously obtained calibration curve. The inherent viscosity () was measured for
solutions containing 0.5 g of polymer in 100 ml in N-methylpyrrolidone (N-MP) using an
Ubellode viscometer at 25 C. The PEIs on the basis of all other monomer pairs (diamine,
dianhydride) were obtained analogously.
2.3. Synthesis of PEI-2 from diamine and tetracarboxylic acid (BAPPBPTA)
0.583 g (1.42 mmol) of BAPP and 0.463 g (1.42 mmol) BPDA and 9.0 g of BA were loaded
into a glass reactor. The process was carried out for 3 h at 140 C, analogously to that for the
dianhydride.
2.4. The kinetics of the CD of the model compound PAA-1 in the melt of BA
Oligomeric amic acid PAA-1 with = 0.13 dl g1 (Mw = 3000) was obtained as described
earlier [18]. For the goal of the measurement of the CD reaction rate, 30 mg of solid PAA-1
and 270 mg of BA were loaded into 10 identical thin-walled glass microtest-tubes which were
all placed into the oil bath simultaneously. In a control experiment, the time to reach 140 C in
every test-tube was estimated, by thermocouple, to be the same: 10 s. At a denite time after
reaching 140 C, the rst, second, etc, test-tube was removed and cooled quickly to 20 C. The
BA was extracted with diethyl ether and the polymer residue was analysed by means of FTIR
spectroscopy (in a pellet of CsI). The conversion by CD was measured from the intensity ratio
of the peaks at 620 cm1 (imide cycle) and 690 cm1 (internal standard) using a previously
obtained calibration curve. The completely cyclicized oligomeric PEI was obtained by heating
the PEI-1 sample in a DSC cell at 300 C at a heating rate of 16 C min1 .

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A A Kuznetsov

2.5. Preparation and analysis of two component polyimidepolyimide formulations

The formulations made ex situ were prepared by dissolution of solid PEI-1 and PEI-7 in the
melt of BA at 140 C. PEI-1 and PEI-7 samples were synthesized separately in the melt of BA
at 140 C for 1 h, each at a 10% load and a 1:1 molar ratio of diamine and dianhydride in the
presence of 1.0% PA as an endcapping agent. The PEI-7/PEI-1 ratio in the mixture was varied
from 0.1:0.9 to 0.9:0.1; the total concentration was equal to 10 wt%. The inherent viscosity
was equal to = 0.35 dl g1 (PEI-7) and = 0.42 dl g1 (PEI-1). After the loading of the
polymers, the mixture was stirred for 1 h, the reaction mixture was then poured into a crucible
and then treated as described above.
The in situ-made formulations were prepared by carrying out the catalytic synthesis of
PEI-7 from HMDA and BPADA (1:1 molar ratio) in the melt of BA at 140 C for 1 h, without
adding any PA. Then PDA and BPADA (1:1) were loaded into the hot reaction medium and
after 1 h PEI-1 was obtained in the presence of PEI-7. The PEI-7:PEI-1 ratio was varied. The
total concentration of PEI-7 and PEI-1 in the reaction mixture was held constant and equal to
10 wt%. The other details of the preparation the sample were the same.
Polymer formulations of both types were hot pressed at 280 C to give pellets. The Tg
values were determined by DSC (DTAP-4, Russia) at a heating rate of 16 C min1 . The data
obtained in a second scan were used to determine the Tg values to elucidate the possibility of
the inuence of a thermal prehistory on the results.
3. Results and discussion
3.1. The melt of BA as a non-toxic catalytic medium for the one-pot synthesis of PEI
BA is known to possess a useful combination of properties: (1) it is a powerful catalyst of the
CD reaction of PAA; (2) as a melt at 140160 C, it is a good solvent for many aromatic PEIs.
Therefore, we propose the melt of BA as alternative solvent for one-pot polyimide synthesis
[18, 19]. An additional advantage of BA appears from consideration of the toxicity data. It is
well known that m-cresol and o-dichlorobenzene (DCB), which are commonly used as highboiling-point organic solvents in high-temperature one-pot polyimide syntheses at 130180 C,
are known to be very toxic substances: the minimal toxic concentrations of m-cresol and DCB
are 5 and 20 mg m1 , respectively. In contrast, BA at ambient temperature is a non-toxic
solid; moreover, in small quantities it is used as a preserving additive for tinned food. Besides
the superiority over m-cresol in toxicity, BA can be easily separated from the polymer after
completing the process. On cooling, the reaction mixture solidies and microphase separation
takes place, BA forming its own crystalline phase. The latter can be easily removed by repeated
washing with acetone.
In gure 1 and gure 2 (curve 1) the kinetics of the inherent viscosity growth of PEI-1
and PEI-2 from a one-pot synthesis in the melt of BA is shown; the starting monomer pairs
were PDABPADA and BAPPBPDA, respectively. The macromolecules PEI-1 and PEI-2
contain the same two hinge fragments of bis-phenol A (BPA) in the elementary chain unit,
but differ from each other by its location: PEI-1 contains a BPA fragment in the anhydride
moiety, whereas PEI-2 contains it in the diamine moiety. In both cases PEI synthesis proceeds
as a homogeneous process throughout all the time of synthesis. In a typical experiment, the
reaction of equimolar quantities of PDA and BPADA at a total of 10% comonomer mixture
load takes about 1 h to give a completely cyclicized product (according to FTIR data) with
= 0.78 dl g1 . The structure and characteristics of several PEIs obtained by us in one-pot
syntheses in the melt of BA are collected together in table 1.
In all cases, values of the inherent viscosity () of about 0.40.5 dl g1 and more were
achieved in 1 h. It should be noted that the level of = 0.5 dl g1 seems to be optimal for a

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449

Figure 1. Kinetics of the growth of the inherent viscosity of PEI-1 from PDA and BPADA in the
one-pot synthesis at 140 C in the melt of BA (total monomer concentration 10 wt%).

Figure 2. Kinetics of the growth of the inherent viscosity of PEI-2 from BAPP and BPDA at 140 C
in different media: (1), the melt of BA; and (2), the melt of BA:DPS, 1:1 mixture (total monomer
concentration 10 wt%).

PEI intended for further melt processing of the PEI. If necessary, the molecular weight of the
PEI can be controlled by the choice of the stoichiometric ratio or by monofunctional additives
such as p-anisidine and PA (gure 3).

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450

A A Kuznetsov
O
C
O

CH 3
O

CH 3
O

C
O

!
C

O
C

O
O

O
C

!

!

Structure 1.
Table 1. Characteristics of PEIs obtained from dianhydrides (structure 1) and diamines of common
formulae H2 NXNH2 in the melt of BA, (140 C for 1 h). Note that the glass transition
temperatures and the melting points are given for the amorphous and crystalline phase, respectively.
Diamine

Dianhydride

PEI

Viscosity () in
N-MP (dl g1 )

Tg
( C)

Tm
( C)

PDA

BPADA

PEI-1

0.78

220

BAPP

BPDA

PEI-2

0.50

240

BAPP

ODPA

PEI-3

0.40

220

BAPP

BPADA

PEI-4

0.48

200

ODA

ODPA

PEI-5

0.42

265

340

ODA

PEI-6

0.52

220

BPADA

PEI-7

0.40

120

165

DDS

BPADA

PEI-8

0.5

230

DAP

SO2

BPADA

HMDA

(CH2 )6

BPADA

PEI-9

0.56

220

PDA:

BPDA

PEI-10

0.50

220

N
+

DAP
(1:1)

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One-pot polyimide synthesis in carboxylic acid medium

451

Figure 3. The inuence of the addition of (1) PA and (2) anisidine as endcapping agents on the
inherent viscosity of PEI-1 (140 C for 1 h).

It is believed that the one-pot polyimide synthesis in BA includes two chemical reactions,
the rst being the acylation of the diamine with the tetracarboxylic acid dianhydrides to give
PAAs, the second being the CD of transient o-carboxyamide moieties to give imide cycles
(scheme 2). The peculiarity of the process in BA is that the rate of CD of transient PAAs
is very high under the conditions chosen. To demonstrate this, we tried to estimate the
CD rate of a model oligomeric amic acid PAA-1 in the melt of BA at 140 C. PAA-1 was
previously synthesized by us for this experiment. The data obtained are presented in gure 4
(curve 1). It is seen that the CD kinetics of PAA-1 in the melt of BA at 140 C is very
fast, too fast for us to calculate accurately the CD rate. However, these data are enough to
conclude that the chain growth in the one-pot synthesis proceeds basically via a polyaddition
reaction of the fully cyclicized oligomers with amino and anhydride end groups. Due to the fast
disappearance of the o-carboxyamide moieties in the course of the CD reaction, the equilibrium
of the polycondensation is shifted continuously to the side of polymer chain growth, and high
molecular weight completely cyclicized PEIs can be obtained in the melt of BA; contrast this
to that in amic solvents at comparable temperatures.
In contrast to the high rate of the CD, the growth rate of the inherent viscosity of PDA
BPADA in BA at 140 C is about the same order of magnitude as that in polycondensation
at 20 C that results in PAA. Taking into account the large difference in temperature (120 C)
between the conditions of polycondensation and the one-pot synthesis in BA, it should be
concluded that diamines in the melt of BA are strongly deactivated, probably due to hydrogen
bonding with BA. As a result, the efcient acylation rate in the melt of BA at 140 C is about
the same as that in the polycondensation reaction in an amic solvent at 20 C. The acylation
rate in the melt of BA is probably much lower than that of the CD reaction; the acylation rate
only is thought to determine the time necessary to obtain completely cyclicized polyimide of
a denite molecular weight.

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A A Kuznetsov

Scheme 2.
P ,%

100

80

60

40
1
20

0
0

10
T im e ,m in

Figure 4. Kinetics of the CD of PAA-I at 140 C: (1) in the solid state; and (2) in the melt of BA.

To conrm the correctness of the proposed mechanism for the process, we investigated
the one-pot synthesis in the melt of BA in the presence of a co-solvent. In gure 2 (curve 2)
the kinetic curve of the inherent viscosity growth in mixtures of BA/diphenylsulfone (DPS)
(50:50 by weight) is shown. The appearance of the viscosity maximum at the start of the

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453

Figure 5. Dependence of the 10 min inherent viscosity value of PEI-2 against the total weight
concentration C of mononers in BA, at 140 C.

process can be explained by the presence of a considerable quantity of o-carboxyamide (amic

acid) moieties in the growing polymer chain, which afford higher hydrodynamic radius to
macromolecules in comparison with that for PEI for an equal degree of polymerization. In
turn, the increased concentration of the transient product in a case of BA/DPS can only be a
result of changing the ratio of the cyclicization/acylation rates in comparison with that in pure
BA. Indeed, the addition of any inert diluent to BA is expected to retard the CD because of the
decrease of the concentration of the cyclicization agent (BA). At the same time, the dilution
will lead to a decrease of the hydrogen bonding of the diamine and BA and, as intended, to
the acceleration of the acylation stage. Moreover, in BA/DPS mixtures, the balance of the
acylation/CD rates is shifted considerably in favour of acylation in comparison with that in
pure BA.
In gure 5, the experimental dependence of the rate of the initial inherent viscosity growth
of PEI-2 against the total monomer concentration is shown. The true reason for the decrease
of the rate at high monomer concentration is not clear. The preliminary supposition is that
this effect is connected with the change of any of the medium characteristics inuencing the
balance of the acylation/CD rates.
3.2. New polyimides and statistic copolyimides from low-reactivity diamines
It can be seen from table 1 that high molecular weight PEIs were obtained successfully
even from low-reactivity diamines such as 4,4-diaminodiphenylsulfone (DDS) and 2,6diaminopyridine (DAP). The low reactivity of the DDS in polycondensation is connected
with its low basicity. DAP is known to possess extremely low reactivity as a nucleophylic
reagent due to occurrence of the aminoimine tautomerism. Furthermore, DAP is known to
give no polyimides under conditions of high-temperature one-pot synthesis in cresol. To check
this, in a control experiment, the reaction between DAP with BPADA (1:1 molar ratio, 10%

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A A Kuznetsov

total monomer load) was carried out by us in m-cresol: after 1 h at 170 C no polymer was
precipitated after adding an excess of methanol. In contrast to this, the high molecular weight
polymer PEI-9 was isolated in quantitative yield after synthesis in BA at 140 C for 1 h.
According to the inherent viscosity data (table 1), the difference in efcient reactivity of
low- and high-reactivity diamines is not observed in the melt of BA, in contrast to that in amic
solvents at ambient temperature. The equal reactivity of highly basic ODA and low basicity
DDS in the melt of BA can be explained by the phenomenon of the equal basicity of strong
and weak bases in acidic media. As concerns the high reactivity of DAP in the BA medium,
the effect observed may be connected with the ability of BA to coordinate the pyridine nitrogen
atom through hydrogen bonding and prevent the aminoimine tautomerism and, hence, lead
to an increase in the reactivity of the amino groups in DAP. Besides, the reactivity equalization
phenomenon in the melt of BA can be useful for obtaining new statistical copolyimides.
To demonstrate this, we made experiments on copolycyclocondensation of BPADA with the
mixture of PDA and DAP (1:1 molar ratio). As can be seen from table 1, a high molecular
weight co-PEI was successfully obtained with = 0.50 dl g1 for 1 h at 140 C. The large
value of the inherent viscosity is evidence for the comparable reactivity of the two diamines
in BA, otherwise the more reactive of these two must be in a large excess of the dianhydride,
resulting in an oligomeric product.

3.3. Regular and alternating copolyimides and block copolyimides

The new approach makes it possible to obtain new regular, alternating and block copolyimides
in the one-pot process. In this work, by means of two-step chain growth in the course of an
in situ consequent catalytic polycyclicization, a series of novel regular PEIs was synthesized.
They consist of two types of polyimide blocks: A and B. Block A being a fragment of PEI1 (an amorphous, thermoplastic and soluble polymer) and block B being a product of the
cyclopolycondensation of PDA and BPDA (a non-thermoplastic and non-soluble polymer, see
structure 2).
As a rst step, the oligomer of the PEI-1 structure with amino end groups was obtained
by cyclopolycondensation of PDA and BPADA taken at molar ratios of 1:0.9, 1:0.85, 1:0.7
and 1:0.6. As a second step, BPDA was added in a quantity corresponding to the overall 1:1
stoichiometric ratio of all amino and anhydride groups, and reaction was continued for 1 h
more (table 2). Theoretically, the synthesis strategy chosen must lead to a so-called regular
copolymer, i.e. to the polymer containing individual fragments of the rst type (in our case
PDABPDAPDA) separated from each other by longer sequences of the other type (in our case
(PDABPADA)n ). Characteristics of the polymeric products obtained are given in table 2.
The values of the glass transition temperature Tg increase smoothly with increasing
numbers of BPDA fragments, from 220 C (PEI-1, sample 1) to 245 C (sample 5). The
samples 24 are soluble in N-MP, sample 5 is soluble only in H2 SO4 . Theoretically, further
increases of the BPDA content in a regular copolymer upto 50:50 BPADA:BPDA ratio must
lead to strongly alternating structures. In this series we met a solubility limitation. However,
it is believed that by the use of appropriate monomers, alternating copolymers are achievable
through the synthesis strategy offered. It should be noted that the fragment (PDABPDAPDA)
which is present in the copolyimides (samples 25) is a long enough rigid block consisting
of six aromatic and heteroaromatic moieties connected without hinge atoms. Therefore, the
regular copolyimides obtained can also be considered as block copolymers. In the future we
intend to apply this strategy to obtain other types of block copolyimides.

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One-pot polyimide synthesis in carboxylic acid medium

455

Structure 2. (a) Block A, PEI-1 and (b) block B, poly-(PDABPDA).

Table 2. Characteristics of regular copolyimides based on PDA(BPDA + BPADA) obtained by a

two-step one-pot synthesis in the melt of BA at 140 C (1 + 1 h)
Sample N

BPDA/BPADA ratio
(mol:%)

Tg by DSC
( C)

Solubility in
N-MP

Inherent viscosity in
H2 SO4 (dl g1 )

1
2
3
4
5
6

0:100 (PEI-1a , control)

10:90
15:85
30:70
40:60
0:100 (control)b

220
225
230
235
245

+
+
+
+
+

0.40
0.35
0.33
0.34
0.34
0.28

a
b

In the presence of 0.5% PA.

The polymer precipitates from the reaction medium.

3.4. Two-component polyimidepolyimide systems with one glass transition temperature

An interesting application of the new synthesis method is the preparation of polyimide
polyimide blends with one glass transition temperature via consequent one-pot polyimide
synthesis in situ of two partially compatible polyimides [21]. Two types of the two-component
formulations (PEI-7/PEI-1) were prepared: the in situ-made formulations and the ex situmade formulations. The in situ-made formulations were prepared by carrying out the
respective catalytic syntheses of PEI-7 and PEI-1 in BA. The mechanically-made formulations
were prepared by the dissolution of separately synthesized PEI-7 and PEI-1 (each in the
presence of PA as an endcapping agent) in the melt of BA. All other details of the preparation
of the samples were kept the same. The phase diagrams were designed for all the formulations
on the basis of the DSC data. In the case of an ex situ-made formulation (gure 6), a clear
microphase separation occurs in a wide interval of PEI-7:PEI-1 ratios from 80:20 to 10:90,
the Tg values for each phase being equal to 140 and 210 C, respectively. In contrast, the

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A A Kuznetsov

Figure 6.
Phase diagram of binary polyimidepolyimide formulations (PEI-1/PEI-7):
mechanically-made formulations (a and b branches); in situ-made formulations (points AE);
and in situ-made formulations with complete endcapping of PEI-7 (points G and F). See text for
further details.

experimental Tg values of the in situ formulations depend on the content; the corresponding
points AE in gure 6 for the in situ-made formulations are located inside the region of the
phase separation of the ex situ-made blends. Thus, the in situ formulations behave as systems
with a molecular level of compatibilization. At the same time, by means of turbidimetry
analysis, the in situ-made formulations were identied as a mixture of homopolymers (or
a long-chain diblock copolymer), but not as a statistical copolymer. In a course of special
experiments using completely end-capped PEI-7, it was shown that the quasi-one-component
morphology behaviour observed in the in situ formulation was caused by the formation of
small quantity of a diblock copolymer playing the role of stabilizer of the polymerpolymer
microemulsion particles and retarding the phase separation. More details will be given in a
separate paper [22].
3.5. Direct polycondensation of diamines and tetra-acids
It is well known that a high quality of comonomers is a very important factor inuencing
the molecular weight of the nal polyimides. In the long-term storage of dianhydrides, the
hydrolysis productsthe corresponding di- and tetra-acidscan accumulate as impurities.
Tetra-acids are not reactive as acylating agents. Therefore, the purication of dianhydrides
and the current control of the quality are strong requirements in usual polyimide chemistry. As
was shown above, the melt of BA can act as a powerful dehydrating agent in relation to amic
acid moieties. Hence, it was suggested that it could serve as an in situ dehydrating agent for
tetracarboxylic acids. In this work we investigated the possibility of using the tetracarboxylic

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457

Figure 7. DSC thermograms of (1) BPTA.2H2 O, (2) BPTA and (3) BPDA.

acid BPTA instead of the dianhydride BPDA in the catalytic synthesis of PEI-2 in the melt
of BA. As can be seen from DCS thermograms of BTPA (gure 7 (curve 2)), anhydridization
of solid BPTA on heating occurs in a region of 250270 C (wide endo peak); the second
endo peak at 300 C corresponds to the melting of the BPDA formed in situ. The second
scan obtained after cooling sample 2 (gure 7 (curve 3)) contains only a peak at 300 C which
coincides with the melting peak of pure BPDA. The temperature of the beginning of the BPTA
anhydridization is much higher than that of the loss of the coordinated water molecules by
BPTA.2H2 O (140170 C) (gure 7 (curve 1)) and higher than the optimal temperature of the
one-pot synthesis in the melt of BA (140 C). To check the suggestion offered above, a series of
experiments were carried out on polyimide synthesis in BA using the tetra-acid BPTA instead
of the corresponding dianhydride (BPDA).
In gure 8 (curve 2) the kinetics of the growth of the inherent viscosity of PEI-2 obtained
from BAPPBPTA at 140 C is shown. It is seen that a high molecular weight PEI-2 with an
inherent viscosity of 0.5 dl g1 was obtained after 3 h, although the chain growth is slower than
that in the case of BPDA (gure 7 (curve 1)). Obviously, the cyclopolycondensation process
of BTDA with BAPP includes the stage of formation of BPDA in situ (scheme 3), the latter
reaction being the rate-determining step in the process as a whole.
3.6. Polycondensation of heteromonomers (AB-type monomers)
The opportunity demonstrated above for the direct polycyclocondensation of diamines and
tetra-acids has reinitiated our interest in AB-type heterocomonomers for polyimides, such as
APPA. According to the data of IR spectroscopy [23], APPA exists in the form of a zwitter ion
(the equilibrium structures in scheme 4).
Intramolecular proton transfer makes AB-type heterocomonomers extremely low in
reactivity in polycondensation reactions. According to [23], they can be converted to
polyimides only by a two-stage synthesis, the rst stage being the direct homopolycondensation
in the presence of (Ph)3 P=O, and the second being chemical imidization. In gure 9 FTIR
spectra are shown of the initial APPA (spectrum 1) and of the oligomeric product (0.20 dl g1 in
H2 SO4 solution) obtained by heating APPA in the melt of BA at 140 C for 45 min (spectrum 2).
The absorption near 16001660 cm1 related to the zwitter-ion structure of APPA disappears

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A A Kuznetsov

Figure 8. Kinetics of the growth of the inherent viscosity of PEI-2 obtained in the melt of BA
starting from pairs of (1) diaminedianhydride (BAPPBPDA) and (2) diaminetetracarboxylic
acid (BAPPBPTA) (140 C, total monomer concentration 10 wt%).

Scheme 3.

Scheme 4.

and the imide peaks at 1720 and 1790 cm1 appear instead. The spectrum of the oligomeric
product obtained in BA is similar to that obtained by polymerization on heating of solid APPA
up to 250 C (gure 9 (spectrum 3)). So, it can be concluded that treatment of AB compounds

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459

Figure 9. FTIR spectra of (1) APPA, (2) the oligomeric product ( = 0.20 dl g1 in H2 SO4 )
obtained by heating the APPA in the melt of BA at 140 for 45 min; and (3) the product (insoluble
in H2 SO4 ) obtained after heating solid APPA at 250 C for 5 min.

in the presence of an acid catalyst at 140 C results in the corresponding PEI (poly-APPA,
gure 9 (scheme 4)), although the molecular weight is not too large. Even more interesting
opportunities appear for the synthesis of linear and star-shaped block copolymers. This work
is also in progress.
4. Conclusion
The main conclusions are as follows.
(1) The melt of BA at 140160 C is shown to be an advanced reaction medium for the catalytic
one-pot process for obtaining high molecular weight, completely cyclicized polyimide
products, including:
(a) thermoplastic PEIs known from the literature;
(b) new polyimides based on low-reactivity diamines;
(c) new statistic copolyimides, containing both high- and low-reactivity diamine
moieties;
(d) new regular, alternating and, probably, block copolyimides;
(e) two-component polyimidepolyimide blends with one glass transition temperature;
(f) PEIs based on AB-type heteromonomers.
(2) The direct polycyclocondensation of diamines with tetracarboxylic acids is demonstrated
to occur in the melt of BA at 140160 C to give high molecular weight completely
cyclicized polyetherimides.

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Acknowledgments
The work was supported by the General Electric Plastics Co. and also by RFBR, grant
97-03-32740. The author also express his thanks to Dr S V Lavrov, Dr V I Berendyaev,
A Yu Tsegelskaya, Dr N V Kozlova, I D Egorov (all from the Karpov Institute of Physical
Chemistry, Moscow), Dr G K Semenova, M Yu Yablokova, L V Ryabova (ISPM RAN), Dr
Belov M Yu (Institute of Problem of Chemical Physics, Chernogolovka) for their participation
in the experimental work; to Professor E L Vulah and Professor M V Dorogov for the synthesis
of the starting materials; and Professor B V Kotov for fruitful discussions of the results.
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