Synthesis of stereospecific hinged ladder polyimides by Diels-Alder reaction

Article abstract of DOI:10.1134/S1070427209020293

A one-stage synthesis of hinge-ladder polyimides by Diels-Alder poly-condensation of polychlorinated cyclic bisimidodienes with bismaleimides containing aromatic and aliphatic groups was studied.

Full text of DOI:10.1134/S1070427209020293

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 2, pp. 323−327. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.S. Salakhov, V.S. Umaeva, A.I. Alikhanova, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 2, pp. 329−333.
MACROMOLECULAR COMPOUNDS
AND POLYMERIC MATERIALS
Synthesis of Stereospecific Hinged Ladder Polyimides
by Diels–Alder Reaction
M. S. Salakhov, V. S. Umaeva, and A. I. Alikhanova
Institute of Polymer Materials, National Academy of Sciences of Azerbaidjan, Sumgaiyt, Azerbaidjan
Received December 12, 2007
Abstract—Aone-stage synthesis of hinge-ladder polyimides by Diels−Alder poly-condensation of polychlorinated
cyclic bisimidodienes with bismaleimides containing aromatic and aliphatic groups was studied.
DOI: 10.1134/S1070427209020293
We know many methods of polyimide synthesis
[1] however they are based mainly on the two-stage
procedures [2] when the second stage is performed by
the thermal way providing difficulties at determination
of a dependence of a structure of amide fragments on
polyimide properties. Besides the hinged polyimides
obtained by the known methods do not possesses 100%
imidization due to an incomplete conversion of the chain
links of polyimide acids [1–3].
since both dienes of a cyclic structure and dienes with
open chain can be applied to the reaction. In this case
a bis-imide of unsaturated cyclic dicarboxylic acid,
bis-maleimide, should be used as dienofil component.
The synthesis of a polyimide (A) via DApolycondensa-
tion of bis-cyclopentadiene with N,N'-(hexamethylene)bis-
maleimide is reported in [4] (Scheme 1), and bis-fulvene
with bis-maleimide in DMF at 60–70°С according
to Scheme 2 resulted in polyimide (B) preparation as
described in [5].
Polymerization by Diels–Alder (DA) reaction is one
of promising trends in the preparation of polyimides of
varios structures that promotes wide modification of the
chemical composition and properties of the polyimides
DApolymerization is important at designing oriented
ladder molecules. However available studies in this
field do not make clear the idea of a spatial structure
Scheme 1.
A
Scheme 2.
B
323

324
SALAKHOV et al.
Scheme 3.
'
Ia, Ib
IIa, IIb
'
IIIa, IIIb
OCH 3
H3CO
(Ib);
R = (CH2)2 (Ia),
CH2
H3CO
(IIa),
OCH 3
'
(IIb).
O
CH2
R =
of the prepared polyimides that firstly is caused by an
absence of proper bis-dienes, whose stereochemistry
can be unambiguously determine the configuration of
the polymer chain fragments [6]. And secondly data
about application of DA polycondensation to halogen-
containing polyimides is absent in literature. Thus in this
paper we suggest one-stage synthesis of hinged ladder
polyimides of desired spatial structure by DAreaction of
chlorinated bis-cyclic bis-imidodienes (Ia, Ib) of known
spatial structure with bis-maleimides (IIa, IIb) that gives
hinged ladder fragments of endo and exo configurations.
In the course of this reaction an formation of side low-
polymeric products is not observed as in the course of
an usual polycondensation and that is an advantage of
this method.
presence of a small quantity of hydroquinone at 150°С
for 6–7 hours due to a good solvating power of initial
monomers and produced polyimides.
The obtained polychlorinated ladder polyimides (IIIа–
IIId) are solid products. Their composition and structure
are confirmed by the data of elemental analysis, and IR
spectroscopy, and also by an authentic synthesis.
The IR spectra of the polyimides IIIа–IIId contain
absorption bands at 1720 and 1780 cm–1 (С=О),
1601 cm–1 (С=С), and 680–720 cm–1 (С–Сl).
The authentic synthesis of the polyimides IIIa–IIId
was performed by diacylation of an apropriate diamine
with bis-imidodianhydride (IVa, IVb) of known spatial
structure in DMF according to Scheme 4, where R and
R' are substituents noted above.
The synthesis of the polyimides was conducted by
one-stage DAreaction of N,N'-(1,2-ehtane)bisimide (Iа)
or N,N'-(3,3'-dimethoxy-4,4'-diphenylmethane)bisimide
of endo,exo-2,3,4,5-tetrachlorobicyclo[4.4.0]deca-2,4-
dien-8,9-dicarboxylic acid (Ib) with bismaleimides (IIа,
IIb) according to Scheme 3.
Characteristics of the polyimides IIIa–IIId obtain-
ed by both methods completely coincide. TG and DTA
indicate (Fig. 1) that the polyimides IIIa–IIId are thermo-
resistant, their destruction starts at 300–350°С, and at
360–400°С they lose only 10% of an initial weight.
The DA polycondensation is fully stereo-specific
course forming the polyimides in whose ladder
maleimide and cyclohexane rings are of endo,endo
DA polycondensation was performed in high-polar
solutions (DMAA, and DMF) that provide homogeneity
of reaction medium, and 100% polycondensation in the
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SYNTHESIS OF STEREOSPECIFIC HINGED LADDER POLYIMIDES
325
Scheme 4.
O
O
O
IIIa, IIIb
IVa, IVb
configuration relative to a rigid bicyclooctane
fragment.
N,N'-(3,3'-Dimethoxy-4,4'-diphenylmethane)-
bisimide endo,exo-2,3,4,5-tetrachlorobicyclo[4.4.0]-
deca-2,4-diene-8.9-dicarboxylic acid (Ib) was
synthesized by method [9]. Yield 90%, mp 293–295°С
(chloroform–hexane). Found, %: С 60.15, Н 3.29, Cl
30.78, N 3.02. С39H30Cl8N2O4. Calculated, %: С 61.65,
Н 3.31, Cl 31.34, N 3.09. IR spectrum, сm–1: 1715, 1780
(С=О), 1605 (С=С), 670–750 (С–Cl).
EXPERIMENT
IR spectra of the synthesized compounds were
recorded on a spectrometer UR-20. Samples were prepared
in a liquid paraffin. A purity was checked by thin-layer
chromatography using benzene–dichloroethane–acetic
acid (8 : 3 : 1.5, by volume) as eluent, spots were detected
under UV light [7].
Thermoresistance measurements was performed
by TGA and DTA methods on a MOM instrument
(Hungery).
Reduced viscosity [η] of 0.5% polyimides solution
was measured on Ubbelohde instrument at 25°С in
dimethylformamide.
N,N'-(4,4'-Diphenyl(oxide)bismaleimide (IIа) was
synthesized by reaction 4,4'-diaminodiphenyloxyde
with maleic anhydride in diethyl ester medium with
subsequent cyclization of the formed amido acid in the
acetic anhydride in the presence of pyridine according
to [8]. Yield 92%, mp 183–185°С. Found, %: С
66.2, Н 2.91, N 7.3. С20H12N2O5. Calculated, %: С 66.7,
Н 3.39, N 7.8.
N,N'-(3,3'-Dimethoxy-4,4'-diphenylmethane)bis-
maleimide (IIb) was synthesized analogously. Yield
90.6%, mp 156–158°С. Found, %: С 66.0, Н 4.3, N 6.7.
С23H18N2O6. Calculated, %: С 65.7, Н 3.89, N 6.3.
N,N'-(1,2-Ethane)bisimide endo,exo-2,3,4,5-tetra-
chlorobicyclo[4.4.0]deca-2,4-dien-8,9-dicarboxylic
acid (Ia) was synthesized by method described in [9].
Yield 80%, mp 223–224°С (chloroform–hexane). Found,
%: С 44.21, Н 2.77, Cl 40.18, N 3.78. С26H20Cl8N2O4.
Calculated, %: С 44.06, Н 2.82, Cl 40.11, N 3.95. IR
spectrum, cm–1: 1710, 1770 (С=О), 1605 (С=С), 670–750
(С–Cl).
Fig. 1. DTA and TG curves of the polyimides IIIa (1) and IIId
(2). (Δm) loss of weight, %, (T) temperature, °С.
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326
SALAKHOV et al.
Fig. 2. IR spectra of the polyimide IIIa on the basis of N,N'-(1,2-ethane)bisimide endo,exo-2,3,4,5-tetrachlorobicyclo[4.4.0]-deca-2,4-
dien-8,9-dicarboxylic acid and of N,N'-(4,4'-diphenyloxyde)bismaleimide. Transmission, %, (ν) wave number cm−1.
Fig. 3. IR spectra of the polyimide IIId on the basis of N,N'-(3,3'-Dimethoxy-4,4'-diphenylmethane)bisimide endo,exo-2,3,4,5-tet-
rachlorobicyclo[4.4.0]-deca-2,4-diene-8.9-dicarboxylic acid and of N,N'-(3,3'-dimethoxy-4,4'-diphenylmethane)bis-maleimide. Trans-
mission, %, (ν) wave number cm−1.
Dianhydrides of endo,endo,endo-2,3,4,5-
tetrachlorotricyclo[6.2.1.05,10]dodec-2-en-7,8-
dicarboxyimide-11,11,12,12-tetracarboxylic acid
(IVа, IVb) was synthesized by method [10]. 10
mmol of N,N'-(1,2-ethane)- (IVа) or N,N'-(3,3'-
dimethoxy-4,4'-diphenylmethane)bisimide endo,exo-
tetrachlorobicyclo[4.4.0]-deca-2,4-dien-8,9-dicarboxylic
acid (IVb) and excess (15–20 g) of the maleic anhydride
was heated at 160°С for 4–6 h. Then this mixture was
poured into chloroform. The separated crystals were
filtered off, washed with chloroform and recrystallized
from a mixture benzene−acetone. Yield (IVа) 90%, mp
302°С. Found, %: С 44.80, Н 2.51, Cl 31.25, N 2.84.
С34H24Cl8N2O10. Calculated, %: С45.13, Н2.65, Cl 31.42,
N 3.09. Yield (IVb) 92%, mp 302°С. Found, %: С 50.91,
Н 2.99, Cl 25.61, N 2.11. С47H34Cl8N2O12. Calculated,
%: С 51.18, Н 3.08, Cl 25.77, N 2.54. IR spectrum, cm–1:
1715, 1780 (С=О), 1605 (С=С), 670–750 (С–Cl).
In 3.54 g (0.005 mol) of N,N'-(1,2-ethane)bisimide
endo,exo-2,3,4,5-tetrachlorobicyclo[4.4.0]deca-2,4-
dien-8,9-dicarboxylic acid (Ia) 1.8 g (0.005 mol) of
N,N'-(4,4'-diphenyloxyde)bismaleimide (IIа), 0.05 g of
hydroquinone and 16 g of absolute dimethylacetamide
were dissolved in a dry three-neck flask equipped with
a stirrer, a thermometer and a reflux cooler with calcium
chloride tube. Concentration of initial components in the
reactive mixture is 25 wt %. A content of the flask was
stirred at 150°С for 6 h. The reactive mixture was poured
into ice water. The separated powder product was filtered
off, washed with water, and then with methanol, and
dried at 60°С. Yield (IIIa) 4.9 g (92%). Characteristic
viscosity [η] = 0.28 dl g–1 (0.5% dimethylformamide,
25°С). Found, %: С 51.02, Н 2.92, Cl 26.15, N 5.04.
С46H32Cl6N4O9 (1:1). Calculated, %: С 51.69, Н 3.00,
Cl 26.59, N 5.24. IR spectrum, cm–1: 1710, 1785 (С=О),
1605 (С=С), 670–750 (С–Cl) (Fig. 2).
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SYNTHESIS OF STEREOSPECIFIC HINGED LADDER POLYIMIDES
327
Polyimide IIIb, 3.54 g (0.005 mol), was obtained
like the previous experiment from 3.54 g (0.005 mol)
of amidobisdiene (Ia) and of 2.09 g (0.005 mol)
of N,N'-(3,3'-dimethoxy-4,4'-diphenylmethane)bis-
maleimide (IIb) at concentration of initial monomers
of 25 wt %. Characteristic viscosity [η] = 0.32 dl g–1
(dimethylformamide, 25°С). Found, %: С 52.00, Н 2.89,
Cl 24.91, N 4.59. С49H38Cl8N4O10 (1:1). Calculated, %:
С 52.22, Н 3.37, Cl 25.22, N 4.97. IR spectrum, cm–1:
1708, 1780 (С=О), 1603 (С=С), 650–750 (С–Cl).
Polyimide IIIc, 4.47 g (92%), [η] = 0.35 dl g–1, was
obtained like the first experiment from 6.33 g (0.005 mol)
of N,N'-(3,3'-domethoxy-4,4'-diphenylmethane)bisimide
endo,exo-2,3,4,5-tetrachloro-bicyclo[4.4.0]deca-2,4-
dien-8,9-dicarboxylic acid (Ib) and 1.8 g (0.005 mol)
of N,N'-(4,4'-diphenyloxide)bis-maleimide (IIа) at
concentration of initial monomers of 25 wt % in
dimethylformamide medium. Found, %: С 55.55, Н 3.00,
Cl 21.99, N 4.02. С59H42Cl6N4O11 (1:1). Calculated, %:
С 55.92, Н 3.32, Cl 22.49, N 4.42. IR spectrum, cm–1:
1710, 1785 (С=О), 1605 (С=С), 670–750 (С–Cl).
Polyimide IIId, 8.20 g (94%), [η] = 0.36 dl g–1 was
synthesized like the first experinment from 6.33 g (0.005
mol) of bisimidodiene (Ib) and 2.09 g (0.005 mol) of N,N
'-(3,3'-domethoxy-4,4'-diphenylmethane)bismale-imide
(IIb) at concentration of initial monomers of 25 wt % in
DMAA medium. Found, %: С 55.88, Н 3.49, Cl 21.11,
N 3.96. С62H51Cl8N4O12 (1:1). Calculated, %: С 56.02,
Н 3.84, Cl 21.38, N 4.21. IR spectrum, cm–1: 1708, 1780
(С=О), 1603 (С=С), 650–750 (С–Cl) (Fig. 3).
polychlorinated bis-imidodienes with bis-maleimides
was developed.
(2) The structure of the synthesized polyimides was
established by IR spectra and the authentic synthesis.
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(1) The one-stage synthesis of the hinge-ladder
polyimides by the Diels−Alder polycondensation of
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