Synthesis and reactivity of metal-containing monomers: 74. Azomethine copper complexes as modifying agents of epoxy matrices

Article abstract of DOI:10.1007/s11172-015-0958-7

The effect of additives of copper azomethine complexes of different structure on the character of polycondensation and physicomechanical properties of the obtained metal-containing epoxy polymers was studied. It was shown by the DSC method that the therma

Full text of DOI:10.1007/s11172-015-0958-7

Russian Chemical Bulletin, International Edition, Vol. 64, No. 4, pp. 936—942, April, 2015
936
Synthesis and reactivity of metalꢀcontaining monomers
74.* Azomethine copper complexes as modifying agents of epoxy matrices
B. A. Komarov,a A. T. Kapasharov,a E. A. Dzhavadyan,a V. A. Lesnichaya,a G. I. Dzhardimalieva,a A. S. Burlov,b
A. I. Uraev,b S. A. Mashchenko,b D. A. Garnovskii,c and A. D. Pomogailoa
aInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation.
Eꢀmail: komarov@icp.ac.ru
bResearch Institute of Physical and Organic Chemistry, Southern Federal University,
194/2 prosp. Stachki, 344090 RostovꢀonꢀDon, Russian Federation
cSouthern Scientific Center,
41 ul. Chekhova, 344006 RostovꢀonꢀDon, Russian Federation
The effect of additives of copper azomethine complexes of different structure on the charꢀ
acter of polycondensation and physicomechanical properties of the obtained metalꢀcontaining
epoxy polymers was studied. It was shown by the DSC method that the thermal stability of the
starting CuII azomethine complexes depended on their structure and nature of polar functional
groups. The physicomechanical properties of the unmodified and modified epoxyamine polyꢀ
mers at different ratios of functional groups were compared. The additives of CuII azomethine
complexes of 0.42—0.43 wt.% were shown to increase the impact strength of the polymers at the
ratio [NH]/EG = 1.07—1.13 (EG is epoxy group).
Key words: copper azomethine complexes, chelate complexes, epoxy resin, metalꢀcontainꢀ
ing epoxy polymers, polymer modification.
Preparation of composites based on complexes with
composites with improved thermal stability and good
physicomechanical characteristics. One of the ways for
achieving these purposes and for imparting new functional
properties can be the insertion (impregnation) of metal
complexes into the structure of crossꢀlinked epoxyamine
polymers. The polycondensation of epichlorhydrin
(1ꢀchloroꢀ2,3ꢀepoxypropane) with ethylenediamine or
oꢀphenylenediamine and introduction of the MnII, CoII,
NiII, and ZnII azomethine complexes, 3ꢀformylꢀ4,4´ꢀdiꢀ
hydroxydiphenylmethane derivatives, gave metalꢀchelatꢀ
ing epoxy polymers with high antimicrobial activity16,17
and thermal stability.18 Thermal stability of epoxy resins
with aromatic chelates is higher than that of the derivaꢀ
tives with aliphatic amines. Macrochelates remain stable
to 325 С, and then a continuous mass loss is observed on
heating to 620 С, indicating the decomposition of the
organic moiety of the polyepoxy complex. Coatings based
on metalꢀcontaining epoxy resins of the considered type
exhibit efficient anticorrosion activity, in particular, this
is characteristic of the ZnII macrochelates on the steel
surface.19
coordinated polydentate ligands is being intensely develꢀ
oped due to their potential application as sensors2,3 and in
nonlinear optics,4 separation and molecular recognition,5
accumulation of gases,6,7 catalysis,8 information and enꢀ
ergy storage, biomedicine, etc. New polymer materials
based on these complexes are most frequently prepared
using various procedures of modifying known polymers,
such as epoxy resins, polyethers, polyurethanes, and others
to impart them new unusual properties or to improve cerꢀ
tain characteristics. It is known that the introduction of
metal/metal complex into a polymer molecule improves
the thermal stability of the polymer.9,10 Catalytic addiꢀ
tives (2 wt.%) of ZnII, CoII, and FeIII acetylacetonates
to sulfosemicarbazide polyurethane increases the temperꢀ
ature of 5% mass loss by 40—50 С.11 The polymerꢀimꢀ
mobilized transition metal complexes with Schiff bases
are well known as efficient catalysts of reaction of oxidaꢀ
tion of olefins and alcohols12,13 and alkene epoxidaꢀ
tion.14,15
Due to prolonged service and high exploitation charꢀ
acteristics, epoxy resins are leading among reactoplasts.
Many areas of their application, such as electronics, airꢀ
craft building, and motorꢀcar construction need epoxy
Special attention is recently given to the synthesis of
novel biꢀ and tridentate azomethine ligands and their metal
complexes. Their structures and properties, including moꢀ
lecular structures, have been described in detail.20—23 The
CuII chelates are most stable. It has previously been
* For Part 73, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0936—0942, April, 2015.
1066ꢀ5285/15/6404ꢀ0936 © 2015 Springer Science+Business Media, Inc.

Azomethine complexes as matrix modifiers
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
937
shown24 that the metal complexes of Schiff bases are effiꢀ
cient precursors of selfꢀorganized nanocomposites stabiꢀ
lized by thermolysis products of the ligand shell of the
complexes.25,26 Since chelates of the considered type with
polar and nonpolar substituents are polyfunctional. It
seemed of interest to study the influence of additives of
copper azomethine complexes of various structure on the
polycondensation processes and physicomechanical propꢀ
erties of the obtained metalꢀcontaining epoxy polymers.
attain a pressure of 0.1—0.2 Torr. Then the molds (for samples
with a size of 80×100×3 mm between the glasses treated with an
antiadhesive) were filled with a free cast. The samples were soꢀ
lidified in the mode: at 100 С for 3 h, at 160 С for 2 h, and at
180 С for 2 h, which made it possible to achieve the maximum
possible conversion for functional groups according to the caloꢀ
rimetric results. The quantitative data on loading all compoꢀ
nents to the reactor of the vacuum mixer are presented in Table 1.
Note that the ratio of functional groups varied from 1.07 to 1.47
(on the average, 1.248) because of losses of the binder compoꢀ
nents, first of all, of the eutectic (its equivalent weight is 5 times
lower than that of the epoxy resin), after sonication with AMC of
different nature. The obtained mixture in an argon flow was
poured to a metallic beaker and cooled in a drying box. The
melting point of the eutectic mixture was ~40 С.
Bis(3ꢀallylsalicylideneꢀ2´ꢀmercaptoanilinato)dicopper(II) (1).
Freshly distilled oꢀaminothiophenol (1.25 g, 0.01 mol) was addꢀ
ed to a solution of 3ꢀallylsalicylaldehyde (1.6 g, 0.01 mol) in
anhydrous toluene (50 mL), and the mixture was heated with
a Dean—Stark trap for 1 h to the complete separation of water.
At the end of the reaction, toluene was distilled off on a rotary
evaporator, and methanol (50 mL) was poured to the residue.
Copper acetate monohydrate (1 g, 0.005 mol) in methanol
(50 mL) was added to the obtained solution. The mixture was
refluxed for 1 h and cooled down. The obtained precipitate of
the complexes was filtered off, washed with boiling methanol
(2×10 mL), and dried in vacuum drying box at 100 С. The yield
was 75%, dark brown powder, m.p. 255—256 С. Found (%):
С, 58.17; Н, 3.89; N, 4.32; S, 10.40. C32H26Cu2N2O2S2. Calcuꢀ
lated (%): С, 58.08; Н, 3.96; N, 4.23; S, 10.66.
Experimental
Materials and reagents. Epoxyꢀdiane resin of Ancarezꢀ728,
Pacific Anchor Chemical (USA), and Epital (analogs of EDꢀ20)
trade marks were used as epoxy binders. An eutectic mixture of
aromatic diamines, mꢀphenylenediamine (MPDA), (Aldrich)
and diaminodiphenylmethane (DADPM) (Aldrich) was used as
a solidifying agent, as well as the Etalꢀ450 amine solidifier of
complicated composition.
Copper acetate monohydrate Cu(CH3COO)2•H2O (reagent
grade) (Reakhim), 3ꢀallylsalicylaldehyde, 5ꢀmethoxysalicylalꢀ
dehyde, oꢀaminothiophenol, phenylacetic acid, aniline, pꢀtoluiꢀ
dine, pꢀbromoaniline, pꢀnitroaniline, acetophenone, pꢀbromoꢀ
acetophenone, pꢀmethylacetophenone, pꢀnitroacetophenone,
ethanol, benzene, DMF, and POCl3 (Aldrich) were used withꢀ
out additional purification. Toluene (pure) was dried over meꢀ
tallic sodium and distilled in argon.
To obtain an eutectic mixture, MPDA (40 g) and DADPM
(60 g) were placed in a 250ꢀmL roundꢀbottom flask. The syntheꢀ
sis was carried out in vacuo on heating to 90—100 С with periꢀ
odical stirring for 1 h. Ultrasonic treatment of the working comꢀ
positions was carried out with a UZDNꢀ1M ultrasonic dispergaꢀ
tor with a working frequency of 22 KHz in a glass ampule (inner
diameter 22 mm), which had the narrowed diameter (17 mm) at
a height of 30 mm and the branch at a height of 70 mm for argon
blowing. This structure makes it possible to use the maximum
power of ultrasonication in a minimum volume of the working
medium.
The vacuum mixer was designed at the Construction Bureau
of the Institute of Problems of Chemical Physics, Russian Acadꢀ
emy of Sciences. An AOLꢀ112 electric motor (1500 rpm) was
combined with a powerful stand using a special corbel. The stand
can be vertically moved with position fixation. The rotor of the
electric motor was made in a closed variant and connected to
a stirrer, the working part of which has a special structure that
makes it possible to provide turbulent stirring of working media.
The motor was connected with a flange and a core to a glass
reactor (useful volume 180 mL) with a jacket for temperatureꢀ
maintaining, a drain vacuum valve, and branches for controlling
vacuum and inert gas filling.
Bis(5ꢀmethoxysalicylideneꢀ2´ꢀmercaptoanilinato)dicopper(II)
(2) was synthesized using a similar procedure from 5ꢀmethoxyꢀ
salicylaldehyde (1.52 g, 0.01 mol), oꢀaminothiophenol (1.25 g,
Table 1. Quantitative data on the load of components of the
epoxy binder modified by AMC additives
AMC
mAMC
(wt.%)
Load to reactor/g
EDꢀ20 AMC+eutectic
[NH]
/EG*
2
1
3
4
5
6
7
0.43
0.40
0.42
0.24
0.43
0.40
0.38
0.52
0.44
0.41
0.43
0.37
0.44
0.40
28.8
27.9
28.8
27.85
28.8
27.51
27.97
27.99
27.99
28.03
28.03
27.77
27.83
28.07
6.30
5.50
5.95
5.17
8.05
5.25
6.47
5.60
7.90
5.44
7.53
5.45
7.87
5.48
1.134
1.020
1.070
0.970
1.089
0.990
1.203
1.040
1.468
1.000
1.397
1.020
1.473
1.010
The epoxy resin in the presence of azomethine additives was
solidified as follows. The calculated amount of the azomethine
complex (AMC) was dissolved in the eutectic (2.2—3.0 g) on
heating (80 С) and ultrasonication for 20 min in an argon flow.
Then the second portion of the eutectic (4—5.5 g) was added and
again ultrasonicated for 5 min. Then the mixture was transferred
to the reactor of the mixer in which a weighed sample of the
epoxy resin (evacuated at 70 С for 15 min to a pressure of
0.1 Torr) was placed. The threeꢀcomponent system was mixed
with stirring (1500 rpm) and evacuation at 70 С for 10 min to
* [NH]/EG is the ratio of functional NH and epoxy groups calꢀ
culated taking into account losses after solidification of an eutecꢀ
tic mixture with AMC for the epoxy number of the Ancarezꢀ728
resin equal to 20% (equivalent weight 215) and the calculated
equivalent weight of the eutectic equal to 40.5.

938
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
Komarov et al.
Scheme 1
3: R1 = R2 = Me
4: R1 = Br, R2 = OMe
5: R1 = NO2, R2 = H
0.01 mol), and copper acetate monohydrate (1 g, 0.005 mol).
The yield was 42%, dark brown powder, m.p. >300 С. Found (%):
С, 52.47; Н, 2.89; N, 4.45; S, 9.85. C28H19Cu2N2O4S2. Calcuꢀ
lated (%): С, 52.58; Н, 2.97; N, 4.38; S, 10.02.
Scheme 2
Azomethine complexes 3—7 were synthesized using earlier
described procedures.25—27
Copper(II) N,N´ꢀdiarylꢀꢀaminovinyliminates (3—5) were
synthesized according to Scheme 1.27
A solution of copper acetate monohydrate (0.2 g, 0.001 mol)
in ethanol (20 mL) was added to a solution containing the
corresponding N,N´ꢀdiarylꢀꢀaminovinylimine (0.68, 0.88, or
0.69 g; 0.002 mol) in anhydrous ethanol (50 mL). The mixture
was refluxed for 2 h. The formed precipitates of the complexes
were filtered off, washed with hot ethanol (2×5 mL), and recrysꢀ
tallized from an ethanol—chloroform (2 : 1) mixture.
Bis(4ꢀmethylꢀNꢀ[(Z,3Z)ꢀ3ꢀ(pꢀtolyl)ꢀ3ꢀ(pꢀtolylimino)propꢀ1ꢀ
enyl]anilino)copper (3). The yield was 45%, dark green powder,
m.p. 187 С. Found (%): С, 77.84; Н, 6.32; N, 7.61. C48H46CuN4.
R = 4ꢀOMeC6H4 (6), Ph (7)
Calculated (%): С, 77.65; Н, 6.24; N, 7.54. IR (KBr), /cm–1
1606 (C=N), 1582 (C=C).
:
Bis(Nꢀ[(Z,3Z)ꢀ3ꢀ(4ꢀbromophenyl)ꢀ3ꢀ(4ꢀmethoxyphenyl)ꢀ
iminopropꢀ1ꢀenyl]ꢀ4ꢀmethoxyanilino)copper (4). The yield was
53%, dark brown powder, m.p. 191—192 С. Found (%):
С, 59.27; Н, 4.45; N, 6.12. C46H40Br2CuN4O4. Calculated (%):
С, 59.02; Н, 4.31; N, 5.98. IR (KBr), /cm–1: 1613 (C=N),
1587 (C=C).
Bis(Nꢀ[(Z,3Z)ꢀ3ꢀ(4ꢀnitrophenyl)ꢀ3ꢀphenyliminopropꢀ1ꢀenyl]ꢀ
anilino)copper (5). The yield was 65%, dark brown powder,
m.p. 210—211 С. Found (%): С, 61.52; Н, 4.38; N, 11.48.
C42H32CuN6O4. Calculated (%): С, 61.41; Н, 4.31; N, 11.23.
IR (KBr), /cm–1: 1613 (C=N), 1587 (C=C).
Copper(II) complexes with phenylmalonodialdehyde dianils
(6 and 7) were obtained by the template synthesis (Scheme 2).28,29
A mixture of ꢀphenylꢀꢀdimethylaminoacrylaldehyde (2.1 g,
0.012 mol), aniline (2.79 g, 0.03 mol) or pꢀanisidine (3.69 g,
0.03 mol), and copper(II) acetate monohydrate (1.2 g, 0.006 mol)
in ethanol (50 mL) was refluxed for 3 h. The precipitates were
filtered off, washed with hot methanol (2×5 mL), and recrystalꢀ
lized from a benzene—ethanol (2 : 1) mixture.
Bis(4ꢀmethoxyꢀNꢀ[(Z,3Е)ꢀ3ꢀ(4ꢀmethoxyphenyl)iminoꢀ2ꢀ
phenylpropꢀ1ꢀenyl]anilino)copper (6). The yield was 40%, dark
green powder, m.p. 252—253 С. Found (%): С, 70.70; Н, 5.40;
N, 7.10. C46H42CuN4O4. Calculated (%): С, 70.98; Н, 5.44;
N, 7.20. IR (KBr), /cm–1: 1601 (C=N), 1569 (C=C).
Bis(Nꢀ[(Z,3Е)ꢀ2ꢀphenylꢀ3ꢀphenyliminopropꢀ1ꢀenyl]anilino)ꢀ
copper (7). The yield was 65%, dark green powder, m.p.
264—265 С. Found (%): С, 76.43; Н, 5.32; N, 8.65. C42H34CuN4.
Calculated (%): С, 76.63; Н, 5.20; N, 8.51. IR (KBr), /cm–1
1607 (C=N), 1573 (C=C).
:
Physicomechanical properties. Samples for tests were preꢀ
pared according to GOST 4647ꢀ80 (ASTM D 1822ꢀ68) (impact
viscosity) and ASTM D 638ꢀ96, D 882ꢀ95a (rupture strength).
The following physicomechanical characteristics were studied:
rupture strength ( ), impact viscosity ( ), relative rupture strain
R
n
( ), and elasticity tensile modulus (Es). The — curves were
R
obtained with a Zwick tensile machine with a deformation rate
of 1 mm min–1. The impact viscosity was determined using
a Zwick impact copra. Strength parameters were measured with

Azomethine complexes as matrix modifiers
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
939
complexes 3—7 have the composition27,28 CuL2. The
characteristic shifts to the longꢀwavelength range by
15—60 cm–1 of the (CH=N) absorption bands in the IR
spectra of complexes 3—7 compared to the initial ligands
indicate their chelate structure.
the accuracy 15% ( ,  , and  ), and the Es values were
measured with the accuracy 4%.
Thermomechanical measurements were carried out on an
UIPꢀ70 instrument (Central Design Bureau, Moscow, Russia)
with a scanning rate of 2.5 С min–1 and a load of 0.2 MPa. The
accuracy of glass transition temperature determination (Tg) in
a range of 130—170 С was 2 С.
A DSC 828 Mettler Toledo differential scanning microꢀ
calorimeter was used to detect DSC data.
Calorimetric tests were carried out using a DAKꢀ1ꢀ1 isoꢀ
thermic calorimeter.
R
n
R
Compounds 2, 3, 5, and 6 have enhanced thermal
stability differed for the complexes depending on their
structure and nature of functional groups. Some characꢀ
teristics of the thermal properties of AMC obtained by the
thermogravimetric and DSC studies are presented in
Table 2. As can be seen from Table 2, the thermal stability
of the examined AMC depends substantially on their comꢀ
position and nature of functional substituents. For examꢀ
ple, complexes 2, 3, and 6 have higher temperatures of
decomposition onset than the complexes bearing reactive
functional groups. The presence of boron atoms, nitro
groups, or double bonds as substituents at the benzene ring
can decrease both the temperature of mass loss onset and
the chemical resistance to the components of the used
epoxy condensation system. Compound 5 contains two
polar methoxy groups in the paraꢀposition, which results
in a low temperature of decomposition onset.
Physicomechanical properties of the native epoxy polyꢀ
mer and the polymer with additives of the azomethine comꢀ
plexes. The physicomechanical properties of the epꢀ
oxyamine polymer at different ratios of functional groups
was studied to establish the effect of influencing AMC
additives.
The results of the tests of the initial and modified samꢀ
ples of the epoxy polymers prepared using the above proꢀ
cedure are presented in Tables 3 and 4. The data in Table 3
clearly demonstrate the substantial dependence of the
physicomechanical properties of the epoxyamine polymer
on the ratio of functional groups: epoxy and NH groups.
Note that any deviation from the equifunctional ratio of
the indicated groups results in polymer plasticization,
which is confirmed by the appearance of forced elastic
Results and Discussion
Synthesis and characterization of the CuII azomethine
complexes. To study the influence of additives of the copper
complexes of different composition and structure (1—7)
on the character of the polycondensation process and
physicomechanical properties of the obtained metalꢀconꢀ
taining epoxy polymers, we chose copper azomethine cheꢀ
lates of two types: copper(II) compounds with Nꢀ, Oꢀ, and
Sꢀtridentate Schiff bases based on 3ꢀallylsalicylꢀ (1) or
5ꢀmethoxysalicylꢀ (2) aldehydes and oꢀmercaptoaniline
and copper mononuclear complexes based on differently
substituted ꢀaminovinylimines with the CuN4 coordinaꢀ
tion node (3—7).
The structures of the complexes were determined preꢀ
viously.23,27,28 The structures of complexes 1 and 2 were
determined from the data of elemental analysis, IR and
EXAFS spectroscopy, and magnetochemical measureꢀ
ments. These complexes include dimeric structures23 with
a strong antiferromagnetic interaction between the copper
atoms (1: 2J = –950 cm–1) with a Cu—Cu distance of
2.96 0.02 Å. According to the elemental analysis data,
Table 2. Thermal properties of the azomethine complexes
a
b
c
AMC
DSC data, Teff/T0
m0
Tdecomp
(wt.%)
/С
endo
exo
1
2
3
4
5
6
7
—
269.9/250
—
241/165
295
294/185
140/110
300
0.96
1.55
1.21
0.33
1.35
—
160
218
180
105
165
260
140
—
286/260
318.3/300
—
334.9
183.9/170
2.42
a Teff/T0 are the temperatures of the endoꢀ and exotherm and the
onset of deviation to an extreme in the Celsium temperaꢀ
ture scale.
b Initial mass loss.
с Temperature of decomposition onset.

940
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
Komarov et al.
Table 3. Physicomechanical properties of the polymers based on
the epoxy resin and solidifying agent, an eutectic mixture of
MPDA and DADPM*
imum glass transition temperature, 166 С, is attained at
[NH]/EG  1.22, while this temperature is ~135 С at the
equifunctional ratio (see Table 3).
It is known30 that the formed hydroxy groups in the
epoxyamine polymers predominantly participate in the forꢀ
mation of intermolecular physical bonds, whose concenꢀ
tration and nature mainly determine the physicomechaniꢀ
cal properties of the epoxy polymer. The concentration of
physical bonds evidently increases with an increase in the
relative concentration of NH groups, thus improving all
strength tensile parameters.
As can be seen from Table 4, additives of the CuII
AMC in a concentration of 0.42—0.43 wt.% result in
a substantial increase in the impact strength of the polymers
(~3 times) only at the ratio [NH]/EG = 1.07—1.13 (see
Table 4). The strength rupture parameters remain almost
unchanged. In essence, small additives of compounds 1,
2, and 3 lead to the same change in the properties as that
observed at the ratio [NH]/EG = 1.5—2.0 for the initial
polymer (see Table 3, entries 9 and 10). This can be due to
an increase in the concentration of physical bonds per unit
volume of the modified epoxy polymer. This increase is
possible due to the formation of new physical bonds of the
AMC molecules with electronꢀdonor centers of the binder
components, first of all, aromatic diamines in which
the AMC are dissolved under the action of ultrasonicaꢀ
tion, or products of the interaction of the AMC with
the components of the epoxy binder, for example, aroꢀ
matic amino groups of the solidifying agent molecules at
80 С and/or during solidification in a temperature range
of 100—180 С.
In addition, the observed phenomenon can be caused
by structural modification at the nanolevel. The dissoluꢀ
tion of the AMC in an eutectic mixture of aromatic diꢀ
amines can result in the formation of complicated associꢀ
ates with the AMC molecules at the center. Mixing with
an epoxy oligomer in a vacuum mixer does not result in
their decomposition but can create the gradient composiꢀ
tion of amino groups between the AMC molecules and,
hence, the gradient distribution of both the chemical crossꢀ
linking density in the crossꢀlinked structure and the coheꢀ
sion energy density of the polymer, which results in the
efficient dissipation of dynamic energy. This is especially
characteristic of the AMC, whose structure contain no
functional groups capable of chemical interacting and
which can be dissolved in a medium of diamines. It is
substantial that modification by this AMC (structure 3)
leads to the highest effect of increasing the impact strength
(see Table 4, Fig. 1). This concept is consistent with the
earlier discovered effect of influencing the concentration
and dispersion of the polymer itself on the temperature of
the polymer based on EDꢀ20—MPDA. It turned out that
the maximum influence on the properties of the polymer
is made by finely dispersed heterogeneous additives, indiꢀ
cating that the properties of the polymer change in both
Entry [NH]
/EG
Еs
MPa



n

Tg/C
R
R
(%) /kJ m–2 (%)
1
2
3
4**
5
6
7
8
9
0.93
0.97
0.99
1.00
1.00
1.15
1.25
1.31
1.51
2.00
2370
2240
2230
2210
2130
1880
1870
1920
1980
2250
89
78
86
75
59
64
76
75
86
93
15.7
15.4
16.7
14.8
13.4
15.0
17.0
16.7
10.7
10.5
10.3
13.4
12.6
11.9
11.6
16.1
12.2
13.5
28.2
46.1
17.2
13.0
20.2
17.6
17.0
17.8
17.1
40.0
20.6
18.0
122
131
129
129
140
163
165
158
144
118
10
* Hereinafter, Еs is the elasticity tensile modulus, R is the rupꢀ
ture strength,  is the relative rupture strain,  is the impact
strength,  is the variation coefficient of impact strength, and Tg
is the glass transition temperature of the polymers.
** The component of the binder were subjected to ultrasonicaꢀ
tion after degassing.
R
n
strain in the tensile diagram (see Table 3, entries 9 and 10).
An extreme dependence of all physicomechanical characꢀ
teristics of the polymer is detected. The minimum of the
strength properties is observed at [NH]/EG  1.22 rather
than at the equifunctional ratio ([NH]/EG = 1). The maxꢀ
Table 4. Physicomechanical properties of the AMCꢀmodified
epoxy polymers based on the epoxy resin and solidifying agent,
an eutectic mixture of mꢀphenylenediamine and diaminodipheꢀ
nylmethane
[NH]/ AMC*
EG
Еs



n

Tg/C
R
R
(%) /kJ m–2 (%)
MPa
1.15
1.01
1.13
1.02
1.07
0.97
1.09
0.99
1.20
1.04
1.47
1.00
1.40
1.02
1.47
1.01
— (US) 1900
— (US) 2080
71
78
68
59
73
78
73
86
86
80
88
58
88
51
87
49
16.0
15.4
15.8
13.8
15.8
15.4
16.1
16.7
10.2
16.0
10.8
13.8
11.0
13.0
10.1
12.8
13.2
11.6
37.4
19.7
38.9
13.4
44.7
12.6
18.8
12.7
25.2
12.6
18.8
12.6
21.0
11.5
10.9
15.8
25.5
17.3
25.0
13.0
10.2
20.1
14.7
16.0
16.5
27.8
19.6
16.2
27.9
31.6
160
133
166
142
147
131
156
129
155
150
147
137
155
140
147
136
2
2
1
1
3
3
4
4
5
5
6
6
7
7
1920
2070
1930
2230
1930
2230
1830
2020
1830
2070
1830
2100
1810
2060
* US is the ultrasonic treatment of components of the binder
after preliminary degassing under similar conditions.

Azomethine complexes as matrix modifiers
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
941
an/kJ m–2
an/kJ m–2
45
50
40
35
30
25
20
15
40
30
20
10
1
2
0.1
0.2
0.3
0.4
0.5
[3] (wt.%)
Fig. 2. Impact strength (аn) of the epoxy polymer Ancarezꢀ728 vs
AMCꢀ3 at the ratio of functional groups [NH]/EG = 1.09—1.16.
1.00
1.28
1.56
1.84
[NH]/EG
Fig. 1. Impact strength (аn) of the epoxy polymer Ancarezꢀ728
(eutectic mixture of aromatic diamines) vs ratio of functional
groups [NH]/EG for the initial system (1) and the system modiꢀ
fied by AMC additives (2).
AMC due to the existence of an optimum average statistiꢀ
cal distance between the AMC molecules uniformly disꢀ
tributed over the binder volume rather than due to the
appearance of gradient properties in the contact zone.
The results of the modification of the epoxy polymer
based on the Epital binder at a solidifying agent concenꢀ
tration of 16.2 and 17.8 wt.% with AMCꢀ3 additives are
presented in Table 6. This epoxyꢀdiane polymer based on
the complicated solidifying of a complicated mixture of
a diamine mixture (Etalꢀ450) is characterized by the imꢀ
provement of all strength tensile parameters: the elasticity
tensile modulus increases by 4—6%, the rupture strength
increases by 35—47%, and the relative rupture strain inꢀ
creases by 17—27%. The glass transition temperature and
impact strength remain almost unchanged.
Thus, the principal possibility of using azomethine
complexes of transition metals as modifiers of the epꢀ
oxyamine polymers based on epoxyꢀdiane resins was exꢀ
perimentally shown. A threefold increase in the impact
strength was found for the ratio of functional groups in the
range 1.05 < [NH]/EG < 1.16 and a additive concentraꢀ
tion of 0.42—0.43 wt.%.
the contact zone and the whole volume with a change in
the topological level of the structural organization of the
polymer. Further studies are planned for the elucidation
of the assumed mechanism in more detail.
A comparison of the obtained data with the properties
of the initial polymer (Table 5) at close (1.09—1.16) ratios
of functional groups shows the improvement of the physiꢀ
comechanical properties of the modified polymers in nearly
the whole studied range of AMCꢀ3 concentrations. The
elasticity tensile modulus increases by 3—16%, and the
rupture strength and relative rupture strain increase by
14—40 and 18—22%, respectively. Note that the glass tranꢀ
sition temperature remains almost unchanged.
The dependence of the impact strength on the concenꢀ
tration of AMCꢀ3 is extreme with a maximum at 0.43 wt.%
(Fig. 2), and the increase is 2.8 times. This can be due to
the fact that the properties of the crossꢀlinked epoxyamine
polymer change upon modification by additives of stable
Table 5. Physicomechanical properties of the epoxyamine polyꢀ
mer based on the Ancarzꢀ728 resin and an eutectic mixture of
aromatic diamines MPDA and DADPM vs concentration of the
modifying additive AMCꢀ3 in a range of 1.09—1.16 of the ratio
of functional groups
Table 6. Physicomechanical properties of the AMCꢀ3ꢀmodified
epoxy polymers based on the epoxyꢀdiane resin Epital and solidꢀ
ifying agent Etalꢀ450
[Etalꢀ450] AMCꢀ3
Еs



n

Tg/C
R
R
(%) /kJ m–2 (%)
[NH]/ [AMCꢀ3]
Еs



n

Tg/C
R
R
wt.%
MPa
EG
(wt.%)
(%) /kJ m–2 (%)
MPa
16.2
16.2*
17.8
0
0.40
0
2590 59
2750 87
2540 66
2650 89
2.9
3.7
3.4
4.0
19.7 10.0
18.9 15.0
11.7 15.0
10.1 18.3
74
73
88
84
1.15
1.11
1.16
1.11
1.09
1.09
0
1880 64
2180 87
2080 89
2140 89
1610 73
2130 90
5.0
5.9
7.0
6.3
6.1
6.6
16.1
7.8
163
0.0038
0.045
0.192
0.43
16.6 16.2 157
16.2 22.4 166
17.2 11.2 159
44.7 10.2 156
15.1 13.2 144
17.8*
0.41
* The data were obtained by the extrapolation of the dependence
of the physicomechanical properties of the epoxyamine polymer
on the concentration of the solidifying agent Etalꢀ450.
0.603

942
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
Komarov et al.
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This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 14ꢀ43ꢀ03580,
13ꢀ03ꢀ12164 ofi_m, 14ꢀ03ꢀ31419 mol_a, and 14ꢀ03ꢀ
00675) and the Presidium of the Russian Academy of Sciꢀ
ences (Program for Basic Research No. 1 "Nanomaterials")
and in the framework of the design part of the state task in
the sphere of scientific activities (Project No. 4.742.2014/K)
in the part of synthesis of metal complexes and study of
their structure.
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I. S. Vasil´chenko, D. A. Garnovskii, G. S. Borodkin, A. D.
Garnovskii, Russ. J. Inorg. Chem. (Engl. Transl.), 2008, 53,
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Received November 11, 2013;
in revised form March 13, 2014