1070-4272/02/7509-1473$27.00C2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 9, 2002, pp. 1473!1476. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 9,
2002, pp. 1505!1508.
Original Russian Text Copyright + 2002 by Amirova, Andrianova, Bukharaev, Fomin.
AND POLYMERIC MATERIALS
Preparation of Polymeric Films with a Gradient of Composition
and Properties across the Thickness from Limitedly Compatible
L. M. Amirova, K. A. Andrianova, A. A. Bukharaev, and V. P. Fomin
Tupolev Kazan State Technical University, Kazan, Tatarstan, Russia
Zavoiskii Kazan Physicotechnical Institute, Kazan Scientific Center, Russian Academy of Sciences,
Kazan, Tatarstan, Russia
Received April 12, 2002
Abstract-Preparation of films from a blend of limitedly compatible epoxy oligomers was considered. The
composition and structure of the films were studied by IR spectroscopy and scanning power microscopy, and
the film asymmetry was demonstrated. The influence exerted by the composition and curing conditions on
the phase separation of the compounds and the structure of the films was revealed.
Polymer3polymer composite coatings structurally
nonuniform across the thickness find growing applica-
tion owing to the possibility of controlling the surface,
interface, and bulk properties of the films .
These goals are commonly accomplished by multi-
layer coating with paint-and-varnish materials differ-
ing in the composition and purpose. However, prep-
aration of such coatings is time- and labor-consuming;
furthermore, additional problems often arise with a
poor adhesion between the layers. Self-segregating
films based on thermodynamically incompatible or
limitedly compatible polymer3polymer, polymer3
oligomer, or oligomer3oligomer compounds are free
of all these drawbacks . Problems related to prep-
aration of asymmetric films from water-dispersible,
soluble, and latex formulations are discussed in .
Of particular interest in this respect are active gly-
cidyl diluents, which are widely used in commercial
production of epoxy lacquers and paints . To obtain
asymmetric films, it is necessary to use diluents that
are limitedly compatible with the epoxy oligomer and
provide controllable distribution of components in the
coatings (e.g., due to different densities).
In this work, we examined the possibility of pre-
paring such asymmetric films from E-40 epoxy34,4`-
isopropylidenediphenol (Dian) oligomer and glycidyl
esters of phosphorus acids. These esters, as shown in
[7, 8], are high-performance active diluents of epoxy
oligomers and allow preparation of polymers with a
high level of service properties (adhesion, softening
point, heat and fire resistance, etc.).
Experiments were performed with E-40 epoxy3
Dian oligomer and the following glycidyl esters of
phosphorus acids (GEPs): triglycidyl phosphate I,
diglycidyl methyl phosphate II, and diglycidyl meth-
ylphosphonate III; their characteristics are listed in
Table 1. As curing agent we used monocyanoethyldi-
ethylenetriamine UP-0633M (stoichiometric coefficient
0.92, viscosity 0.2 Pa s at 25oC, density 1.1 g cm
The compatibility of ED-40 with GEPs was evalu-
ated microinterferometrically with an MI-2 device ,
and the phase diagrams were constructred. The surface
tension was determined by the Du Nouy method from
the force of detachment of a platinum ring. The size
and size distribution of emulsion droplets were evalu-
ated from the turbidity spectra [10, 11]. Optical meas-
urements were performed with an SF-26 spectropho-
tometer. The viscosity of epoxy oligomer mixtures
was measured with a Hoeppler viscometer.
Coatings from E-403GEP compounds, 803100 mm
Table 1. Characteristics of epoxy oligomers*
Oligomer ³ EN, % ³ M ³ r,gcm
E-40 ³ 14.1 ³ 800 ³ 1.178
I ³ 48 ³ 266 ³ 1.3673
II ³ 38 ³ 224 ³ 1.3140
III ³ 41 ³ 208 ³ 1.2789
* (EN) Epoxy number, (M) molecular weight, and (r) density.