ISSN 1995-4212, Polymer Science, Series D. Glues and Sealing Materials, 2008, Vol. 1, No. 3, pp. 158160.

Pleiades Publishing, Ltd., 2008.

Original Russian Text A.I. Zagidullin, R.M. Garipov, M.V. Kolpakova, O.V. Stoyanov, 2008, published in Klei. Germetiki. Tekhnologii, 2008, No. 1, pp. 1719.

Structure and Properties of Epoxy Composites Cured

with New Organosilicon Amines
A. I. Zagidullin, R. M. Garipov, M. V. Kolpakova, and O. V. Stoyanov
Kazan State Technological University, ul. Karla Marksa 68, Kazan, 420043 Tatarstan, Russia
e-mail: ov_stoyanov@mail.ru; svf@ksaba.ru
Received October 12, 2007

AbstractThe results of the curing of bisphenol A-based epoxy oligomers (ED-20 and NPEL-128) with silicon-containing amines (SCAs) synthesized by the interaction between bifunctional alcohols with different
molecular masses and -aminopropyltriethoxysilane (AGM-9) are reported. It is shown that, in the case of using
SCAs, epoxy oligomer is cured more completely and a higher degree of elasticity in the polymer matrix is
achieved without using modifiers, which is impossible in the case when polyethylene polyamines are used.
DOI: 10.1134/S1995421208030052

The use of different curing agents in compositions

based on epoxy oligomers leads to the formation of a
polymer matrix with different topological structures. In
cases when cure occurs under natural conditions, the
formation of a crosslinked polymer is complicated by
the fact that the reaction system can be transformed into
a glassy state, thus leading to the termination of cure at
the incomplete consumption of functional groups [1]. It
was shown previously [2] that the use of silicon-containing SCA-1 amine as a curing agent permits us to
increase the content of gel fraction and improve physicomechanical properties of coatings compared to coatings cured with traditional agents. Therefore, the
expansion of the assortment of silicon-containing
amines capable of forming polymer matrix upon the
cure of epoxy resins with maximal conversion of functional groups is an urgent problem.
As curing agents of epoxy compositions, we used
diethylenetriamine (DETA), triethylenetetramine
(TETA), and organosilicon amines, products of condensation of -aminopropyltriethoxysilane with different dibasic alcohols. Epoxy oligomers ED-20 (Russia)
and NPEL-128 (Nan Ya, Taiwan) were chosen as curing
systems.
Glass transition temperatures Tg of the samples were
determined from thermomechanical curves obtained at
constant loading under compression [4]. Effective
crosslink density nc was determined by the modified
ClaffGledding method at a temperature exceeding the
glass transition temperature by 50C [4]. Polymer density was measured by the hydrostatic method [5].
Impact strength was measured using a U1-A instrument; bending strength was measured by the ShG-1
bending scale; and relative hardness was measured with
an M-3 pendulum instrument. Adhesion of cured compositions was determined by the scratch tests [6].

Silicon-containing amines synthesized by the interaction between 2 mol of -aminopropyltriethoxysilane

(AGM-9) and 1 mol of bifunctional alcohols with different molecular masses such as diphenylsilane diol
(SCA-1), bisphenol A (SCA-2), diethylene glycol
(SCA-3), and triethylene glycol (SCA-4), were used as
curing agents that form crosslinks with functionality
equal to three. Products obtained were colorless transparent liquids whose characteristics are shown in
Table 1.
Compounds synthesized were identified by IR spectroscopy and by determining the concentration of
amine groups. In the IR spectra of the obtained products, intense absorption bands at 10301100 cm1 typical of SiOSi and SiOC bonds were observed; at
1590 and 30403060 cm1, bands characteristic of aromatic nuclei were observed. Bands attributed to
hydroxyl linked with silicon are absent and bands corresponding to NH2 groups are seen at 3300 and
3400 cm1 [7].
Studies of structural and topological organizations
of polymer network demonstrated that thermomechanical curves (Fig. 1) have a pattern that is classical for
Table 1. Characteristics of synthesized curing agents

158

Curing
agent

Content
of NH2
groups, %

20, cP

20

nD

d4 ,
g/cm3

M,
kg/kmol

SCA-1

5.6

1.496

39.1

1.174

566

SCA-2

5.45

1.506

219.3

1.065

578

SCA-3

7.0

1.4475

29.1

1.425

456

SCA-4

6.35

1.445

31.9

1.034

500

20

STRUCTURE AND PROPERTIES OF EPOXY COMPOSITES CURED

159

Deformation, mm
0.5
0

50

150
200
Temperature, C

0.5
2

1.0

crosslinked polymer; i.e., a jump is observed upon the

transition from the glassy to rubbery state. Afterwards,
only heat-induced elongation of the samples takes
place.
As can be seen from Table 2, when using SCAs, a
rather large decrease in glass transition temperatures is
observed as compared to the traditionally used curing
agents, which is associated with the appearance of flexible siloxane fragments in the polymer structure [3].
As a result of the substitution of flexible aliphatic
chains in a molecule of curing agent for rigid aromatic
fragments, compositions cured with SCA-3 and SCA-4
under standard conditions are in a rubbery state compared to SCA-1 and SCA-2. The effective crosslink
density of the polymer matrix obtained using SCA at
100C is much lower as compared to the case when
DETA or TETA are used as curing agents. This fact is
explained by the structure of the molecule of the curing
agent in which nitrogen atoms forming crosslink nodes
are located at a fairly long distances from one another,
in contrast to ethylene amine-type curing agents, which
is reflected in an increase in the molecular mass

Tg , C

ED-20 + SCA-1
ED-20 + DETA
NPEL-128 + SCA-2
NPEL-128 + SCA-3
NPEL-128 + SCA-4
NPEL-128 + TETA

52
108
51
<20
<20
109

POLYMER SCIENCE

In case of using SCAs, epoxy oligomer is cured to

greater extent. This is confirmed by the IR spectra of
samples cured at room temperature (Fig. 2). The IR
spectrum of a composition cured by DETA displays an
absorption band at 920 cm1, which is typical of epoxy
groups [7], thus testifying to the incomplete consumption of epoxy groups. In the IR spectrum of the composition cured with organosilicon curing agent, this
absorption band is absent (Fig. 2).
Table 3 presents physicomechanical properties of
studied compositions. As is seen from these data, the
use of organosilicon curing agents makes it possible to
prepare coatings with high elasticity, flexibility, and
adhesion, except for SCA-2, whose structure contains
rigid benzene fragments. Moreover, it is necessary to
note that, upon the curing of epoxy oligomer with given
curing agents, a high degree of elasticity in the polymer
matrix is achieved, which is impossible in the case
when polyethylene polyamines are used.
Table 3. Physicomechanical properties of compositions

Composition

Table 2. Topological characteristics of cured samples

Composition

between crosslinks Mc when silicon-containing curing

agents are used.

nc ,
Mc ,
, kg/m3
kmol/m3
kg/kmol
1.83
2.43
1.575
1.75
1.297
2.478

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483.9
605.7
660.6
898.2
487.7

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ED-20 + SCA-1
ED-20 + DETA
NPEL-128 + SCA-2
NPEL-128 + SCA-3
NPEL-128 + SCA-4
NPEL-128 + TETA

Adhesion
of coating, points

Fig. 1. Thermomechanical curves of samples based

on ED-20 and NPEL-128 oligomers cured with
SCA-1, DETA, and TETA at 100C.

Fig. 2. IR spectra of film samples based on ED-20 oligomer cured with (1) SCA-1 and (2) DETA.

Impact
strength by U-1
method, cm

2.0

920 cm1

Film elasticity
at bending, mm

NPEL-128 + TETA
ED-20 + SCA-1
ED-20 + DETA

ME-3 hardness
of coating,
arb. units

1.5

0.92
0.89
0.85
0.33
0.43
0.78

3
15
12
2
1
12

50
30
40
50
50
25

1
2
2
1
1
3

160

ZAGIDULLIN et al.

REFERENCES
1. V. I. Irzhak, B. A. Rozenberg, and N. S. Enikolopyan,
Polymer Networks (Nauka, Moscow, 1979) [in Russian].
2. R. M. Garipov, M. V. Kolpakova, A. I. Zagidullin, et al.,
Lakokras. Mater. Ikh Primen., Nos. 78 (2007).
3. M. V. Sobolevskii, O. A. Muzovskaya, and G. S. Popeleva, Properties and Applications of Organosilicon Products (Khimiya, Moscow, 1975) [in Russian].
4. A. A. Askadskii, Structure and Properties of Thermostable Polymers (Khimiya, Moscow, 1981) [in Russian].

5. A. M. Toroptseva, K. V. Belgorodskaya, and V. M. Bondarenko, Laboratory Manual on Chemistry and Technology of Polymers (Khimiya, Leningrad, 1972) [in Russian].
6. M. I. Karyakina, Laboratory Manual on Testing Paint
and Varnish Materials and Coatings (Khimiya, Moscow,
1977) [in Russian].
7. K. Nakanishi, Infrared Absorption Spectroscopy (Holden
Day, Tokyo, 1962; Mir, Moscow, 1965).

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2008