CONTENTS

Diene Condensation Based on Dienophiles of Maleic Series

I.G. Ayyubov ……………………………………………………………………………………………………… 331

Oxidative Dehydrogenation of Ethylbenzene in Styrene on MgO,ZrO2/Al2O3 Catalyst

M.T. Mammadova ................................................................................................................................. 347

Influence of the Reaction Conditions on the Gas-phase Polymerization Process of Butadiene in the
Presence of Heterogenized Cobalt Dithiophosphate Catalysts
S.S. Salmanov …………………………………………………………………………………………………….. 356

Increasing the Efficiency of the Process Oil Formation by Heat Methods

F.F. Mammadov …………………………………………………………………………………………………. 373

Impact of Sequence of Chloropropoxy- and Propoxy-Units on Petrocollecting Capacity of

Surfactants Based on Lauric Acid
A.Z. Abilova ………………………………………………………………………………………………………. 383

Reactivity of -Diketonates of Metals with Variable Valencies and Their Nitroderivatives in Liquid-
Phase Oxidation Reaction of Naphthenic Hydrocarbons
L.I. Aliyeva, L.M. Efendiyeva, N.N. Babanly, A.D. Kuliyev, V.M. Abbasov……………………………… 389

Deactivation of AlCl3-containing Catalyst Complex of the Alkylbenzenes Production

by Epoxy-containing Compounds in the Ultrasonic Field
E.Sh. Bayguskarova, R.A. Akhmedyanova, L.A. Zenitova…………………………………………………... 401

Research of Lowinox 22ib46 Inhibiting Properties and It's Test as a Potential Anti-Oxidizing
Additive for Diesel Fuel
Y.P. Cherepnova ………………………………………………………………………………………………… 409

Influence of Metal-Containing nanofiller ob rheological properties of mixed Thermoplastic

elastomers on the basis of isotactic polypropylene and ternary ethylene-propylene-diene elastomer
N.I. Kurbanova, N.A.Alimirzoyeva, N.B. Arzumanova, N.T.Kakhramanov .......................................... 417

Optimization of Phenol Cycloalkylation Process with Cyclohexene in the Presence of Catalyst

KU-23
I.I. Alekperova, Z.Z. Aghamaliyev, F.M.Veliyeva, Ch.K. Rasulov ………………………………………… 424

Group Hydrocarbon Composition of the Mixture of Straight- Run Diesel Fraction with Light Gas
Oil Coking Before and After Purification of Ionic-Liquid Extraction
M.J. Ibrahimova, V.M. Abbasov, S.A. Seyidova, A.E. Alizadeh, H.D. Huseynov ………………………. 433
PPOR, Vol. 20, No. 4, 2019, pp. 417-423

INFLUENCE OF METAL-CONTAINING NANOFILLER ON RHEOLOGICAL

PROPERTIES OF MIXED THERMOPLASTIC ELASTOMERS ON THE BASIS OF
ISOTACTIC POLYPROPYLENE AND TERNARY ETHYLENE-PROPYLENE-DIENE
ELASTOMER
Nushaba I. Kurbanova, Nahida A. Alimirzoyeva,
Nushaba B. Arzumanova, Najaf T. Kakhramanov
Institute of Polymer Materials of Azerbaijan National Academy of Sciences,
Sumgait, AZ 5004, S. Vurghun Str., 124
e-mail: kurbanova.nushaba@mail.ru
Abstract
The influence of additives of the nanofillers containing nanoparticles of
copper oxide, stabilized by polymer matrix of high pressure polyethylene,
prepared by mechano-chemical method on rheological properties of
mixed thermoplastic elastomers on the basis of isotactic polypropylene
and ethylene-propylene-diene elastomer has been investigated. The
viscosity, shift rate, shift tension and also activation energy of viscous
flow of the compositions. It has been shown that in filling of the polymer
mixture polypropylene/ethylene-propylene-diene elastomer with nano-
particles of the copper oxide at low temperatures it is observed a regime
close to Newtonian regularity of melt flow, which is disturbed at
temperature rise. A view of rheological curves evidences about
pseudoplastic character of their flow with appearance of viscosity
anomaly – by viscosity decrease in increase of shift rate characteristic for
majority of polymers. It can be established on the basis of prepared
results of investigation that the activation energy of viscous flow of the
composite filled with nanoparticles of the copper oxide is lower than
initial mixture polypropylene/ethylene-propylene-diene elastomer. The
obtained data show the possibility of reprocessing of nanocomposites by
methods of high-speed molding under pressure. It has been shown by a
method of scanning electron microscope that an introduction of the
copper-containing nanofillers into polypropylene/ethylene-propylene-
diene elastomers leads to the formation of finely spherulitic layered
structure of filled composition and thereby improvement of fluidity and
rheological properties
Keywords: metal-containing nanofiller, thermoplastic elastomers, isotactic polypropylene,
ethylene-propylene-diene elastomer, rheological properties
Introduction
In recent years, the polymer nanocomposites attract the great attention of researchers due
to the improved complex of their exploitation properties. An availability of nanofillers in
polymer matrix leads to an improvement of mechanical [1–4], thermal [5,6], electrical [7,8] and

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rheological properties [9] of the polymers.

Among polymer compositions the mixtures on the basis of polyolefins and rubbers take an
important place. In content of rubber up to 50-90% there are formed the principally new
materials – thermoplastic elastomer (TPE), which combine mechanical properties of rubbers at
usual temperatures with ability to reprocessing, characteristic for linear thermoplastic polymers
higher their melting point [10-13]. In spite of the fact that TPE substitute traditional rubbers, in
literature there are limited numbers of works devoted to study of their rheological behavior.
The purpose of this work – investigation of structure and peculiarities of rheological
properties of the nanocomposite polymer materials on the basis of isotactic polypropylene (PP)
and ternary ethylene-propylene-diene elastomer (SKEPT) with use of metal-containing
nanoparticles (NP) stabilized on polymer matrix as nanofillers (NF).
Experimental Part
In work there have been used: isotactic PP of mark TPPF79FB (Russia) with melting flow
index 10÷15 g/10 min, Vicat softening temperature (10H) not more 150°С; SKEPT of mark Hüls
with ρ = 0.86 g/cm3, containing 8 % ethylidene norbornene.
NPs of the copper oxide I (Cu2O), stabilized on polymer matrix of industrial high pressure
polyethylene, prepared by mechano-chemical method in polymer melt were used as NF. A
content of nanoparticles – 5 mas. %, size – 251.0 nm, degree of crystallinity – 35÷45% [14]. A
ratio of components of the polymer mixtures (mas. %): PP/SKEPT/NF = 50/50/1.0.
The nanocomposite polymer materials have been prepared by mixing of PP with SREPT
and copper-containing NF on laboratory rollers at tempertaure 160-165°С for 15 min. Further the
prepared mixtures were pressed as the plates by thickness 1mm at 190°С and pressure 10 MPa.
The rheological properties of the polymer materials melt were measured in accordance
with [15] on capillary rheometer of mark CEASTMF50 (firm INSTRON, Italy), which
determines the following properties: viscosity, shift rate and shift tension. The rheometer has
been equipped with nozzle having capillary length-to-diameter ratio equal – 24. The
measurements were carried out at four temperatures (from 190 to 250°С) and five loads (from
3.8 to 21.6 kg), because in accordance with experimental statistics this is a minimum quantity of
experimental points, which provide for actuality of conclusions about process [16].
SEM-analysis of the prepared compositions has been carried out on apparatus ZEISS
(Germany).
Results and Discussion
With expansion of possibilities of making the large-size automobile parts by high-speed
molding under pressure, the requirements for the rheological characteristics of the polymer
compositions are appeared in the foreground [17, 18]. With the expansion of the production of
large-size automotive parts by high-speed injection molding, in the foreground are the
requirements for the rheological characteristics of polymer compositions
From this point of view it was interesting to establish how the mixing process of SKEPT
with isotactic PP and NP of the copper oxide can influence on change of their rheological
characteristics.

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In Fig.1(a,b) the flow curves of the considered polymer mixture PP/SKEPT and composite
on its basis of PP/SKEPT/NF.
It is seen from rheogram listed in Fig. 1(a,b) that at low temperatures the flow curves have
a linear character and at relatively high temperatures a linear dependence of shift rate on shift
stress is disturbed. It can be seen from comparative analysis of flow curves that in filling of the
polymer mixture PP/SKEPT with nanoparticles of the copper oxide at low temperatures it is
observed a regime close to Newtonian regularity of melt flow, which is disturbed at temperature
rise. Analyzing rheogram of the polymer mixture PP/SKEPT and its composite filled with NP of
copper oxide, one can establish the influence of metal-containing NF on shift rate, i.e. at content
of NP of the copper oxide (1.0 mass p.) in the mixture PP/SKEPT it is observed some growth of
melt shift rate of composite.

a) b)

Fig.1. Dependence of shift rate on shift stress а) PP/SKEPT; b) PP/SKEPT/NF at various

temperatures: ○-190°C; ×-210°C; ●-230°; ▲-250°C
In Fig. 2(а,b) in logarithmic coordinates the dependences of effective viscosity on shift rate
and temperature for initial thermoelastoplas on the basis of PP/SKEPT at ratio 50/50 and its
composite filled with NP of copper oxide are presented. A view of rheological curves presented
in Fig.2 (а,b) evidences about pseudoplastic character of their flow with appearance of viscosity
anomaly – by viscosity decrease in increase of shift rate characteristic for majority of polymers.
One can seen analyzing the curves presented in Fig.2 (а,b) that the composite viscosity
filled with nanoparticles is lower than viscosity of the corresponding unfilled composite.

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a) b)
Fig.2. Dependence of melt viscosity а) PP/SKEPT; b) PP/SKEPT/NF on shift rate at various
temperatures: ○-190°C; ×-210°C; ●-230°; ▲-250°C
For estimation of activation energy of viscous flow it has been constructed the plot in
coordinates lgη – 1000/T. According to Frenkel-Eyring theory a viscosity exponentially depends
on temperature. In a case of nonlinear dependence of viscosity logarithm on inverse temperature
it is calculated so called apparent activation energy of flow [18]. In this connection in Fig.3(а,b)
the results of investigation of influence of inverse temperature on effective viscosity of mixture
PP/SKEPT and its composite filled with NP of the copper oxide are presented. These
investigations were carried out in the wide range of loads: from 3.8 to 21.6 kg.
In Fig.3 (а) the curves of dependence of melt viscosity on inverse temperature for polymer
mixture PP/SKEPT are presented. It is evidently seen from these curves that in the ranges of
loads from 3.8 to 21.6 kg a viscosity dependence on temperature has a nonlinear character and an
apparent activation energy of viscous flow is changed in the ranges of 11.87-22.83 kJ/mol.

а) b)
Fig.3. Dependence of melt viscosity а) PP/SKEPT; b) PP/SKEPT/NF on inverse temperature at
various loads: ○- 3.8 kg; ×-5.0 kg; ●-10.0 kg; □-12.5 kg;▲-21.6 kg

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In Fig.3 (б) the curves of dependence of melt viscosity on inverse temperature for
composite PP/SKEPT/NF are presented. It is evidently seen from these curves that in the ranges
of loads from 3.8 to 21.6 kg a viscosity dependence on temperature has a nonlinear character and
apparent activation energy of viscous flow is changed in the ranges of 7.75-11.03 kJ/mol.
It can be established on the basis of prepared results of investigation that the activation
energy of viscous flow of the composite filled with NP of the copper oxide is lower than initial
mixture PP/SKEPT.
A heterogeneous system PP/elastomer/filler has a complex structural morphology due to
possibility of simultaneous existence of 3 types of separation surface: PP-elastomer, PP-filler,
elastomer-filler [19,20]. In principle, in such systems two boundary structures can be formed: 1 –
separate distribution of particles of elastomer and filler in PP matrix; 2 – encapsulation of filler
particles by elastomer. Naturally, in reality in the composites PP/elastomer/filler, these two
structures always exist simultaneously, the dominant of which is determined by thermodynamic
and kinetic factors [19]. The formation of structure with encapsulation of filler particles by
elastomer is more advantageous from thermodynamic point of view, since it requires less energy
for viscous flow.
SEM-analysis of the prepared nanocomposites has been carried out (Fig.4 а,b).
In Fig.4(а) the microphotography of the inital mixrture PP/SKEPT is presented. It is seen
that the structure of the composite is compact spherulite. An introduction of nanofiller (NF) into
the composition of the mixture favors the formation of more fine spherulitic layered structure,
which leads to an increase of fluidity of the nanocomposite and thereby improvement of the
rheological properties (Fig.4-b).

а b
Fig.4. SEM – images of the sample structures: a - PP/SKEPT, b - PP/SKEPT/NF
Conclusions
The new nanocomposites on the basis of PP/SKEPT with use of the copper-containing
nanofiller prepared by mechano-chemical method, stabilized by polymer matrix of high
presasure polyethylene have been obtained.

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N.I. KURBANOVA, N.A. ALIMIRZOYEVA, N.B. ARZUMANOVA, …

SEM-analysis of the prepared nanocomposites has been carried out. An introduction of NP

of the copper oxide in polymer leads to the formation of a fine spherulitic layered structure,
favoring the improvement of properties of the prepared nanocomposites has been shown.
It has been revealed the improvement of melting flow index and rheological properties,
which shows the possibility of its processing by methods of high-speed molding under pressure.
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Received: 08.04.2019.

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