ISSN 1996-4196

Chemistry
&
Chemical
Editor-in-Chief
Michael Bratychak Technology

Volume 1 ? Number 2

LITTERIS ET ARTIBVS

Lviv Polytechnic
2007 National University
 Chemistry
&
Chemical Technology
Volume 1 · Number 2
2007
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© Lviv Polytechnic National        L. Pidlisecka, I. Pastyrska, O. Sidorchuk, I. Sopronuyk, I. Stelmah,
University, 2007
Editorial Board
Prof. Michael Bratychak, Lviv Polytechnic National
University, Ukraine – Editor-in-Chief
Prof. Volodymyr Starchevskiy, Lviv Polytechnic National
University, Ukraine – Deputy Editor-in-Chief
Dr. Olena Shyshchak, Lviv Polytechnic National University,
Ukraine – Executive Secretary
Prof. Zoryan Pich, Ukraine
Prof. Stanislav Voronov, Ukraine
Prof. Victor Yavorskiy, Ukraine
Prof. Miroslav Malyovaniy, Ukraine
Prof. Volodymyr Novikov, Ukraine
Prof. Iosyp Yatchyshyn, Ukraine
Prof. Roman Gladyshevskiy, Ukraine
Prof. Boris Zimenkovskiy, Ukraine
Prof. Valeriy Shevchenko, Ukraine
Prof. Witold Brostow, USA
Prof. George Broza, Germany
Prof. Victor Castano, Mexico
Prof. Elizabete Lucas, Brazil
Prof. Witold Waclawek, Poland
Program Board
Prof. Myron Lozynskiy, Ukraine
Prof. Grigoriy Kovtun, Ukraine
Prof. Stepan Kuchmiy, Ukraine
Prof. Iosyp Opeida, Ukraine
Prof. Olexander Yurchenko, Ukraine
Prof. Mikhailo Burmistr, Ukraine
Prof. Grigoriy Gryn', Ukraine
Prof. Ulf Gedde, Sweden
Prof. Vera Kovacevic, Croatia
Prof. Ram Singh, India
Prof. Aglaia Vassilikou-Dova, Greece
Prof. Sergiy Ivanchev, Russia
Acknowledgements
M. Bus'ko, S. Goloshchuk, N. Golovko, L. Laitaruk, O. Mazur, I. Myskiv,
N. Vodarska, O. Yarema
 CONTENT

Chemistry

Zoryan Pikh
Oxidation of unsaturated aldehydes by different oxidants 61
Alexander Zaichenko, Natalya Mitina, Kateryna Rayevska, Taras Skorohoda, Jan Zawadiak,
Danuta Gilner, Volodymyr Lobaz and Volodymyr Novikov
Design of polymers of block, comb-like and highly branched structures with peroxide- 71
containing chains
Yuliya Voloshyna, Lyubov Patrylak, Ivan Manza and Angela Yakovenko
Influence of zeolite crystals external surface modification on toluene para-dispro-
portionation selectivity 79
Ananiy Kohut, Roman Fleychuk, Orest. Hevus and Stanislav Voronov
Macroinitiators on the basis of new peroxide surface active monomers 83
Oleg Suberlyak and Volodymyr Skorokhoda
The peculiarities of the polyvinylpyrrolidone copolymers synthesis for contact lenses 87

Chemical Technology

Yevgen Kovalov
Production and quality of blast furnace coke in Ukraine 91
Leonid Zhelezny, Yevgen Kobylyansky and Oleg Mishchuk
Influence of nature of dispersed phase on antiwear properties of high temperature
greases 97
Yaroslav Vakhula, Victor Vasijchuk, Anna Romaniv and Oleg Semchuk
Peculiarities of formation of sol-gel coatings based on water glass 103
Sergey Boychenko, Oksana Vovk, Larisa Chernyak and Ksenya Akinina
Quality and ecological safety of motor fuels 109

iii
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 1, No. 2, 2007 Chemistry

Zoryan Pikh

OXIDATION OF UNSATURATED ALDEHYDES

BY DIFFERENT OXIDANTS
Lviv Polytechnic National University,
12 Bandera Str., Lviv, 79013, Ukraine
pikh@polynet.lviv.ua
Received: May 10, 2007

Abstract. The new data about oxidation of unsaturated
aldehydes of a general structure R–CH = C(R)–CHO by
molecular oxygen (in liquid and gaseous phase), peracids
and hydrogen peroxide were obtained. The composition
of reaction products for a series of aldehydes with different
structures was determined. The dependencies of the
selectivity of reaction from an aldehyde structure and
oxidant type have been evaluated. It has been assumed
that a stage of aldehyde interaction with peracid determines
the formation of reaction products. The common
mechanisms of unsaturated aldehydes oxidation by
different oxidants have been established on the basis of
generalization of obtained results.
Key words: oxidation, unsaturated aldehyds, peracids,
hydrogen peroxide, oxygen
1. Introduction
The oxidation of unsaturated aldehydes is an
attractive pathway for obtaining unsaturated acids.
Aldehydes can be easily oxydized by molecular oxygen,
and the oxidation process of acetaldehyde is an important
industrial method for production of acetic acid and its
anhydride. [1]
Due to the specific chemical structure of unsaturated
aldehydes their oxidation leads to the formation of by-
products. The presence of two reactive centres in the
molecule of unsaturated aldehyde which can undergo
oxidation (carbonyl group and C=C double bond) leads to
the change of the reaction rate and selectivity as compared
to saturated analogues. The above mentioned effects are
strongly influenced by the localization of both carbonyl
group and C=C double bond in the molecule of aldehyde
as well as presence of substitutions. In the case when
carbonyl group and double bond are well separated in the
aldehyde molecule they behave as independent reactive
centres providing formation of carbonyl, carboxyl, epoxy
compounds and products of epoxide ring opening. [2,3]
In the case when reactive centres are localized
closely they influence each other by varying the oxidation
rate and selectivity. Additionally, such aldehydes and
corresponding acids undergo polymerization during
oxidation. This makes the optimization of the highly
selective methods for production of unsaturated acids very
difficult. [2]
Two ways for the oxidation of unsaturated
aldehydes are frequently reported in the literature: oxidation
in the gas phase by using oxide catalyst and oxidation in
liquid phase. In both cases complicated mechanisms and
formation of the by-products have been reported. The
experimental data reported in the literature can be hardly
compared due to the specific reaction conditions and
different approaches for data analysis.
The detailed studies of the reaction products as
well as generalization of the oxidation principles of
unsaturated aldehydes with different oxidants allowed us
to determine common features and peculiarities of different
oxidation methods and to control selectivity of investigated
processes.
2. Results and discussion
2.1. Oxidation of unsaturated aldehydes
by peracids
It has been determined experimentally, [4-8] that
during oxidation of unsaturated aldehydes (acrylaldehyde,
methacrylaldehyde, 2-ethylpropenal, crotonaldehyde,
2-ethyl-2-hexenal) with peracetic acid beside unsaturated
acid and acetic acid (originated from peracetic acid) some
by-products have been formed such as formates,
epoxyformates and products of their further transfor-
mations (Table 1).
62 Zoryan Pikh

Table 1
Compounds formed after oxidation of unsaturated aldehydes with peracetic acid

3URGXFWQDPH &KHPLFDOIRUPXODH
0HWKDFU\ODOGHK\GH
0HWKDFU\OLFDFLG + &&+±&22+
,VRSURSHQ\OIRUPDWH + &&+±2±&+2
±0HWK\O±±HSR[\HWK\OIRUPDWH &+±&&+±2±&+2
2 
$FHWRQH &+±&2±&+
$FHWLFDFLG &+&22+
)RUPLFDFLG +&22+
(WK\OSURSHQDO
±(WK\OSURSHQRLFDFLG + &&+±&22+
±(WK\OHWKHQ\OIRUPDWH + &&+±2±&+2
±(WK\O±±HSR[\HWK\OIRUPDWH &+±&&+±2±&+2
2 
±%XWDQRQH &+±&2±&+
3URSLRQLFDFLG &+ &22+

)RUPLFDFLG +&22+
&URWRQDOGHK\GH
&URWRQLFDFLG ± + &+±&22+
±3URSHQ\OIRUPDWH ± + &+±2±&+2
±(SR[\SURS\OIRUPDWH ±&+±&+±2±&+2
2 
3URSLRQDOGHK\GH &+ & 2
3URSLRQLFDFLG &+ &22+

$FHWLFDFLG &+&22+
)RUPLFDFLG +&22+
(WK\OKH[HQDO
±(WK\O±±KH[HQRLFDFLG  ± + &&+±&22+
±(WK\O±±SHQWHQ\OIRUPDWH  ± + &&+±2±&+2
±(WK\O±±HSR[\SHQWHQ\OIRUPDWH  ±&+±&  ±2±&+2
2 
±+HSWDQRQH &+±&2±&+
3URSLRQLFDFLG &+ &22+

%XW\ULFDFLG &+  &22+

 Oxidation of Unsaturated Aldehydes by Different Oxidants 63

Following mechanism of product formation has been proposed based on the structure of the identified compounds
in the reaction mixture [6]:

5 2 2
,
 5&+ & &  5 & 
2+ 2+
5 2 2
5&+ & &  5 &
+ 22+
5 2 2
,,
5&+ & 2 &  5 & 
+ 2+

5 2 2 5 2
,,,
5&+ & 2 &  5 & 5&+ & 2 &  5&22+ 
+ 22+ 2 +

2 2
Wƒ
5&+ &5 2 & 5&+ &5 2+ 5&+ & 
B
+ &2 5

2 2
5 & 5 &  2
22+ 2+

2
+
5&+ &5 2 &  +2 5&+ &5 2+  +&22+ 
+
2
,9
5&+ &
5
5 2 2
5&22+ 5&22+  5&22+  &2 
5&+ & 2 &  5 &
2 + 22+

The proposed mechanism indicates that interaction Table 2

of unsaturated aldehydes with peracetic acid took place The selectivity of the unsaturated acid formation
by two pathways: oxidation of the carbonyl group leading during oxidation of unsaturated aldehydes
to formation of unsaturated acid (reaction 1); integration with peracetic acid
of oxygen between carbon atoms in unsaturated aldehyde at the degree of conversion 0.9 (T=303 K)
leading to formation of formate of unsaturated alcohol
$OGHK\GH 6HOHFWLYLW\
(reaction 2). Both pathways are related to the Bayer-
%\DOGHK\GH %\SHUDFLG
Williger mechanism for unsaturated aldehydes. The
formate of unsaturated alcohol further decomposes to &URWRQDOGHK\GH  
ketone (reactions 4,5) or is subjected to epoxidation ±(WK\OSURSHQDO  
(reaction 3). The formed epoxyformate according to 0HWKDFU\O
 
reaction 3 is further oxidized by peracid (reaction 6) leading DOGHK\GH
to unsaturated acids. The selectivity of the unsaturated ±(WK\O±±
 
acid formation is determined by the relation of reaction KH[HQDO
rates (steps 1 and 2).
64 Zoryan Pikh

Figures 1 and 2 represent kinetic curves for reagent Table 2 indicates that the selectivity of the
consumption and product accumulation during oxidation unsaturated acid formation is lower for the aldehydes with
of 2-ethylpropenal and 2-ethyl-2-hexenal respectively. The the alkyl substitutents in a-position relatively to carbonyl
experimental data indicate that peracid is consumed faster group or in a,b-positions compared to crotonaldehyde
compared to aldehyde due to the participation of the peracid having alkyl substituent in b-position. According to the
in reactions (3) and (6). The experimental curves for the selectivity of the unsaturated acid formation by oxidation
reaction products correlate with proposed reaction with peracids aldehydes can be positioned in following
mechanism. order: crotonaldehyde (2-butenal) > 2-ethylpropenal >
The experimentally determined selectivity values for methacrylaldehyde (2-methylpropenal) > 2-ethyl-2-
unsaturated acid during oxidation of unsaturated aldehydes hexanal. Lower selectivity of the unsaturated acid formation
are presented in Table 2. by oxidation of methacrylaldehyde compared to 2-
ethylpropenal is related to the polymerization ability of
&PROO methacrylaldehyde and methacrylic acid.
 The presented data for the oxidation of unsaturated
aldehydes by peracids indicate formation of by-products
 and the selectivity of the unsaturated acid formation is
determined by the aldehyde structure.


2.2. Liquid-phase oxidation

of unsaturated aldehydes by oxygen

 The oxidation of unsaturated aldehydes by molecular
  oxygen in the liquid phase has been studied in the
temperature range 293 – 313 K. All experiments have been
 WPLQ carried out in thermostated bubble reactor. Following

   
products of the oxidation process have been identified:
-for a-alkyl substituted unsaturated aldehydes
Fig. 1. The kinetic curves for reagent consumption and
5
product accumulation during oxidation of 2-ethylpropenal 2
&+ & &
with peracetic acid in benzene (T=313 K): 2+
1 – 2-ethylpropenal; 2 – peracetic acid; 5&2&+
2
3 – 2-ethylpropenoic acid; 4 – 1-ethylethenyl-1-formate; 5 &+ &5  2 &
2 2
5 – 1-ethyl-1,2-epoxyethylformate &+ & & 5&22+ +
2
+ &+ & 5 2 &
+
2
&PROO
 &2&2
+&22+

 -for crotonaldehyde 2
&+ &+ &+ &
2+
 &+&+&22+
&+&+&+2
2 2 +&22+
 &+ &+ &+ & 2
+ &+ &+ &+ 2 &
  +
  2
 &+ &+ &+ 2 &
+
 2
WPLQ &2&2

    Along with unsaturated acid the unsaturated alcohol
and corresponding epoxide, carbonic acids, ketones and
Fig. 2. The kinetic curves for reagent consumption and carbon oxides are formed during oxidation of the
product accumulation during oxidation of 2-ethyl-2-hexanal unsaturated aldehyde with oxygen. The main reaction
with peracetic acid in benzene (T=313 K): 1 – 2-ethyl-2-
pathway is following radical mechanism determining the
hexenal; 2 – peracetic acid; 3 – 2-ethyl-2-hexenoic acid;
4 – 1-ethyl-1-pentenylformate; 5 – 1-ethyl-1,2- formation of the reaction products. However, the primary
epoxypentenylformate molecular product of the aldehyde oxidation is peracid
which is formed according to reactions 7-9.
 Oxidation of Unsaturated Aldehydes by Different Oxidants 65

The formed peracid reacts with starting aldehyde leading to unsaturated acid and by-products (see part 1). The
by-products can be formed additionally during radical transformation stages following another way of the peracyl
radical interaction with aldehyde:

5 2 5 2
5&+ & &  2 5&+ & &  +2 (7)
+
5 2 5 2 (8)
5&+ & &  2 5&+ & &
22

5 2 5 2 5 2 5 2
5&+ & &  5&+ & & 5&+ & &  5&+ & & (9)
22 + 22+

The selectivity of the unsaturated acid formation during aldehyde oxidation with molecular oxygen is low due to
the formation of the by-products by two different pathways.

5 2 5 2 5 2 5 5 5 5
5&+ & &  5&+ & & 5&+ & & 2 2 &+ & 2 2 &+ & 2
22 +
& &
2 + 2 +
5
5&+ & &22+  Q 5 &22+  Q+&22+

&PROO 2.3. Oxidation of unsaturated aldehydes



by hydrogen peroxide
 The unsaturated acids can be obtained during
 oxidation of unsaturated aldehydes by hydrogen peroxide.
In the case of unsaturated aldehydes the interaction with
 hydrogen peroxide takes place in the presence of catalyst
 (compounds of Se, Te, W, Mo, Ti, Ce, Sb) [11]. As a
 model system the oxidation of unsaturated aldehydes with
 hydrogen peroxide in the presence of H7[P(Mo2O7)6]×H2O

 [12] has been used to study the reaction products.

In the presence of this catalyst the reaction is fast,
 however many by-products are formed:
 WPLQ

 -for a-alkyl substituted unsaturated aldehydes
     5
2
&+ & &
Fig. 3. The kinetic curves of product formation during 2+
5 5 & 2 &+
oxidation of 2-ethylpropenal by molecular oxygen at 303 K: 2 +2 2
&+ & & &+ & 5  2
1 – 2-ethylpropenoic acid; 2 – propionic acid; 3 – formic &
+ +
acid; 4 – 1-ethylethenyl-1-formate; 5 – 1-ethyl-1,2- +&22+
2
epoxyethylformate; 6 – peroxides; 7 – total acidity 5 & &
2+
2
For example the selectivity of the unsaturated acid -for 2-butenal
formation at 303 K at 50% conversion is 37.7%, 42.5%, 2
&+ &+ &+ &
70%, 53% for methacrylaldehyde (2-methylpropenal), 2- 2+
ethylpropenal, crotonaldehyde (2-butenal) and 2-ethyl-2- &+&+&+2
2
hexenal respectively. &+ &+ &+ &
+2
+&22+
The kinetic curves of the product formation during + 2
&+ &+ &+ 2 &
oxidation of 2-ethylpropenal by molecular oxygen are 2 +
presented in Figure 3. +& &
2 2+
66 Zoryan Pikh

The given by-product list indicates that as the (or aldehyde), unsaturated formate, acetic acid and keto-
consequence of the unsaturated aldehyde oxidation by (or aldehyde) acids are formed.
hydrogen peroxide corresponding unsaturated acid, ketone

&PROO E
&P ROO
 

 

 
 
 
  
 
 
 
 
WPLQ 
WP LQ
 
         

Fig. 4. The kinetic curves for products (a) and reactants (b) during oxidation
of 2-ethylpropenal by hydrogen peroxide in the presence of H7[P(Mo2O7)6]×H2O:
1 – 2-ethylpropenal; 2 – hydrogen peroxide; 3 – 1-ethylethenylformate;
4 – 2-oxobutanoic acid; 5 – 2-ethylpropenal;
6 – acetic acid (solvent – dioxane; T = 323K)

Fig. 4a indicates that aldehyde and hydrogen
peroxide are consumed in non-equivalent amounts. The
kinetic curves for reaction products have characteristic
shape of continuous reactions. The formation of the
reaction products characteristic for the oxidation of
unsaturated aldehydes with peracids indicates principal
similarity to oxidation mechanisms by hydrogen peroxide.
The difference between two oxidants is only presence of
the catalyst which is required to transform oxygen from
hydrogen peroxide to aldehyde. [12]
The overall scheme of the catalytic oxidation of
unsaturated aldehydes with hydrogen peroxide according
to [13, 14] can be presented as follows:

+2NDW > @

2 +2 2 +2 2
&+ &5 & &+ &5 & 5 & &
2 2+ 2+ 2+
&+ &5 & > @ 2+ 2+ 2
+ 2 +2
&+ & 5  2
According to this mechanism, hydrogen peroxide
interacts with catalyst forming a peroxy-form of a catalyst
[PC]. The [PC] further reacts with aldehyde leading to
the simultaneous formation of unsaturated acid and
unsaturated formate. The formation of the by-products
& 5& 2 &+  +&22+
+
is possible by a) hydroxylation of unsaturated acid with
further oxidation of the product to ketoacid and formic
acid and b) hydrolysis of the unsaturated formate with
formation of ketone and formic acid.
 Oxidation of Unsaturated Aldehydes by Different Oxidants 67

2.4. Vapour-phase oxidation and methacrylic acid formation by using Fe-Te-Mo-O

catalyst is 82.8% and 58.8% respectively.[16] Additionally
of unsaturated aldehydes by using
the reaction rate of the methacrylaldehyde oxidation is
heterogeneous catalysts two times higher compared to acrylaldehyde.
The formation of the reaction products has been It has been determined [17] that heterogeneous
studied for the oxidation of unsaturated aldehydes in gas catalysts with the phosphomolibdenic heteropolyacids
phase with water vapour and Mo12PCs2Pb0.72Ox as catalyst (PMA) exhibit better selectivity toward formation of
in the temperature range 583-613 K. Following unsaturated acid formation during oxidation of
mechanisms have been established for oxidation of methacrylaldehyde. The oxidation efficiency of Mo-ions
acroleine and methacroleine: in PMA increases with increase of the electronegativity
for the second cation: P > As > Si.
2
&+ &+ &  2 The reaction rate and selectivity of the aldehyde
+ oxidation process on heterogeneous catalysts depends on
the unsaturated aldehyde structure. It has been determined
[18] that the reaction rate of the oxidation process for
&+&+2 &2
2 unsaturated aldehydes increases in the line:
&+ &+ &
2+ methacrylaldehyde (2-methylpropenal) > 2-ethylpropenal
> 2-propylpropenal > acrylaldehyde (propenal) (catalyst
Mo 12PCs 2Pb 0.72O x; T=580K). The selectivity of the
&+&22+
unsaturated acid formation at similar conversion increases
in the following way: 2-ethylpropenal > 2-propylpropenal
> 2-methylpropenal > propenal. The increase of the
&2&2 +2
selectivity with aldehyde molecular weight can be related
to the influence of the substituent on the coupling of double
bond and carbonyl group.
&+
2 The presented above interpretation of the unsatu-
 2
&+ & & rated aldehyde oxidation processes with heterogeneous
+
catalysts is based on classical theories of heterogeneous
&2 &2 catalysis. The important issue is the relation of the
&+
2 mechanisms for the unsaturated aldehyde oxidation in the
&+&2&+ &+ & & liquid an gas phases. We made an attempt to correlate the
&+&+2 +&22+
&2&2 +2
&+&22+
It is known [15] that the oxidation of aldehydes in
gas phase follows Red-Ox mechanism and the oxygen
integrated into the crystal structure of the catalyst
participates actively in this process. At the first stage of
the reaction reagents adsorb on the catalyst surface. The
adsorbtion of unsaturated aldehydes on the catalyst surface
can occur by carbonyl group or C=C double bond.
Therefore, the adsorbtion efficiency of above mentioned
reactive centres determines the selectivity of the
unsaturated acid formation during oxidation of such
aldehydes.
It is common that the selectivity of the unsaturated
acid formation during oxidation of propenal and 2-
methylpropenal is different even at similar reaction
conditions. For example the selectivity of the acrylic acid
2+
experimental studies of the mechanisms for two processes
which have been previously judged from completely
different positions. The similarity of the final reaction
products is obvious for two oxidation processes; therefore
we assume that during the oxidation by using
heterogeneous catalyst the composition of the reaction
products is determined by peroxy-compounds of catalyst.
Let’s consider possible ways for the occurrence
of the peroxy-compounds on the surface of solid catalyst.
It is known [19] that the interaction of the O2- and O- ions
(formed during adsorbtion of the oxygen on the catalyst’
surface) with double bond of the aldehyde can lead to the
formation of surface-attached peroxy-complexes. The
formation of surface-attached peroxy-compounds is also
possible due to the reaction of heteropoly acids of
molybdate with oxygen. [11,20] These facts indicate the
high probability of the product formation during oxidation
of unsaturated aldehydes in the presence of heterogeneous
catalysts occurs with participation of peroxides. The best
evidence for this is a good correlation of the reaction
product composition for the oxidation of unsaturated
aldehydes in the presence of heterogeneous catalysts by
hydrogen peroxide and peroxy acids. The mechanism of
the product formation during the oxidation with
68
heterogeneous catalysts can be explained considering
results of the oxidation of unsaturated aldehydes with
hydrogen peroxide in liquid phase in the presence of
molybden-containing catalysts. It is clear that more
extreme reaction conditions during the oxidation with
heterogeneous catalyst and presence of the water vapour
eliminate some intermediate products (formates,
epoxyformates, peroxides).
This interpretation of the oxidation processes gives
a possibility to formulate a new approach to the selection
of the heterogeneous catalyst: the effective catalysts must
have components able to create surface-attached peroxy-
compounds with certain oxidation ability and stability. The
best catalysts in terms of selectivity should be compounds
able to create stable enough peroxy-complexes with mild
oxidation power.
3. Conclusions
The complex approach for the studies of
unsaturated aldehyde oxidation with different oxidants
allowed creation of the general mechanism for oxidation
processes.
1. The experimental results indicate that the
oxidation of unsaturated aldehydes is a complex process
where different oxidation mechanisms coexist (radical and
molecular processes of the oxidation with oxygen,
hydrogen peroxide and peracids).
The general scheme of the unsaturated aldehyde
oxidation is presented below:
2 aldehydes with oxygen in liquid phase is possibility of the
Zoryan Pikh
of the pathways for the product formation in different
oxidation methods. The oxidation processes are
complicated and often different oxidation processes occur
simultaneously.
For example, the oxidation of unsaturated aldehydes
with molecular oxygen occurs by radical mechanism under
participation of carbonyl group and is accompanied by
molecular interactions of unsaturated aldehydes with per
acid and hydrogen peroxide. Additionally, polymerization
processes take place as well as reactions of radical
transformations with participation of C=C double bond.
During interactions of unsaturated aldehydes with
peracid beside the oxidation of carbonyl group another
process takes place, namely epoxidation of intermediate
formates of unsaturated alcohols. During catalytic oxidation
of unsaturated aldehydes with hydrogen peroxide the
oxidation of carbonyl group is accompanied by
hydroxylation of C=C bond leading to the formation of
the destructive oxidation products. In all three oxidation
methods the key role plays reaction of aldehyde with
peracid in terms of the product formation.
3. During oxidation of unsaturated aldehydes with
molecular oxygen numerous by-products are formed. This
effect has following reasons: a) variability of the reaction
between aldehyde and peroxy acid; b) the peracyl radical
can participate in the chain extension reaction by elimination
of the hydrogen from carbonyl group and addition to C=C
bond and formation of less active radical; c) presence of
the peroxides with different reactivity in the reaction
mixture.
The main problem of the oxidation of unsaturated
&+ &5 &
+ addition of peracyl radical to the double bond of aldehyde,
what induces polymerization processes. Therefore, the
2 contradiction exists between radical mechanism of the
5&222+ oxidation reaction and selectivity of the unsaturated acid
+2NDW formation.
Another specialty of the oxidation processes with
participation of molecular oxygen is formation of the by-
  products in the reaction mixture with much higher
reactivity as compared to the main reagents. For example,
the presence of saturated aldehydes in the reaction mixture
2 2 leads to the fast consumption of saturated aldehyde during
&+ &5 & &+ &5 2 & oxidation process. The radicals formed by this process
2+ + are much more active regardless carbonyl group and C=C
bond. Therefore such reaction must be considered as
simultaneous oxidation of substances with different
reactivity. Additionally, one should keep in mind another
way of the oxidation process if reaction mixture contains
%\SURGXFWV hydrogen peroxide and carboxylic acids. In this case the
transfer of the active oxygen from hydrogen peroxide to
2. The systematic studies of the oxidation processes substrate occurs through the formation of peracid. This
for unsaturated aldehydes with different chemical structure is the reason why carboxylic acids are better solvents for
led to the important conclusion about principal similarity the oxidation of aldehydes with oxygen.
 Oxidation of Unsaturated Aldehydes by Different Oxidants
4. The oxidation of unsaturated aldehydes with
hydrogen peroxide in the presence of catalyst is closely
related to the oxidation with peracids since the oxidant
for the aldehyde is inorganic peroxy acid formed due to
the interaction of catalyst with hydrogen peroxide.
Therefore the oxidation scheme is similar to the oxidation
with peroxy acids. The peculiarity f this reaction is possible
hydroxylation of C=C bond in the presence of different
catalysts. This leads to destructive oxidation of aldehyde.
A special position among catalysts possesses Se-based
compounds [14] which provide high reaction rates and
selectivity. The reasons for high selectivity in this case
are: a) optimal balance between oxidation strength and
stability of Se-peroxide complex and b) formation of the
intermediate complex with aldehyde which provides
stabilization of carbon backbone of the aldehyde.
References
[1] Maslov S., Blumberg E.: Uspechy Chimij, 1976, 45, 303.
[2] Haines A.: Method for the oxidation of organic compounds.
Academic press, 1986.
[3] Rubailo V.and Maslov S.: Liquid-phase oxidation of
unsaturated compounds. Ìoskwa, Chyimia, 1989.
[4] Pikh Z.: Dopovidi NAN Ukraine, 1996, 3, 116.
[5] Pikh Z., Kucher R, Iatchishin J.and Gunka M.: Neftechimia,
1983, 23 (3), 368.
[6] Pikh Z., Purig Ia., Iatchishin J. and Horvaty I.: Zhurn. Organ.
Chem., 1979, 15 (12), 2459.
[7] Pikh Z. and Samaruk V.: Zhurn. Organ. Chem., 1993, 29 (8),
1553.
[8] Pikh Z., Fedevich M. and Samaruk V.: Dopovidi NAN
Ukrainy, 1993, 11, 144.
[9] Pikh Z., Fedevich M., Iatchishin J. and Tolopko D.:
Dopovidi NAN Ukrainy, 1976, 11 (B), 1001.
[10] Pikh Z., ,Samaruk V.and Kuptsevich O.: Dopovidi NAN
Ukrainy, 1991, 6 (B), 121.
69
[11] Woldman G.: Zhurn. Anorg. Chem., 1977, 22, 2498.
[12] Pikh Z.,Kosmyna N., Samaruk V. and Sheredko A.:
Neftechimia, 1991, 31 (3), 322.
[13] Pikh Z., Denys G. and Iatchishin J.: Zhurn. Organ. Chem.,
1979, XV (9), 1831.
[14] Pikh Z.,, Samaruk V. and Chajkyvskij T.: Dopovidi NAN
Ukrainy, 1991, 7 (B), 125.
[15] Margolis L.: Oxidation of hydrocarbons on heterogeneous
catalysts. Ìoskwa, Chimia, 1977.
[16] Zhuznevskyj V.,Fedevich E.,,Nykypanchuk M., Golub I.,
Iakubovska L.and Shupailo V.: Chem. Technol., 1979, 1, 30.
[17] Chugaev V. and Sagalovich V.: Dopovidi NAN Ukrainy,
1980, 11, 114.
[18] Zhuznevskyj V., Grumaliuk B. and Agbosu S.: Zhurn. Phys.
Chim., 1984, 58 (12), 2968.
[19] Haber J.: Prz. Chem., 1980, 59 (2), 64.
[20] Volnov I.: Peroxocomplex by chrom, wolframum, tungstan.
Ìoskwa, Nauka, 1989.
ÎÊÈÑÍÅÍÍß ÍÅÍÀÑÈ×ÅÍÈÕ ÀËÜÄÅòIJÂ
вÇÍÈÌÈ ÎÊÑÈÄÀÍÒÀÌÈ
Àíîòàö³ÿ. Îäåðæàíî íîâ³ äàí³ ïðî îêèñíåííÿ
íåíàñè÷åíèõ àëüäåã³ä³â çàãàëüíî¿ áóäîâè R–CH=C(R)–CHO
êèñíåì (ó ð³äê³é òà ãàçîâ³é ôàç³) ã³äðîïåðîêñèêèñëîòàìè òà
ïåðîêñèäîì âîäíþ. Âñòàíîâëåíî ñêëàä ïðîäóêò³â îêèñíåííÿ
àëüäåã³ä³â ð³çíî¿ áóäîâè òà âèÿâëåíî çàëåæí³ñòü ñåëåêòèâíîñòè
ðåàêö³¿ â³ä áóäîâè àëüäåã³äó òà îêñèäàíòó. Ïîêàçàíî, ùî
âèçíà÷àëüíîþ ó ôîðìóâàíí³ ñêëàäó ïðîäóêò³â ðåàêö³é îêèñíåííÿ
º âçàºìîä³ÿ àëüäåã³äó ç ã³äðîïåðîêñèêèñëîòîþ. Óçàãàëüíåíî
îäåðæàí³ ðåçóëüòàòè ³ çàïðîïîíîâàíî ñõåìè óòâîðåííÿ
ïðîäóêò³â ïðè îêèñíåíí³ íåíàñè÷åíèõ àëüäåã³ä³â ð³çíèìè
îêñèäàíòàìè.
Êëþ÷îâ³ ñëîâà: îêèñíåííÿ, íåíàñè÷åí³ àëüäåã³äè,
íàäêèñëîòè, ïåðîêñèä âîäíþ, êèñåíü.
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 1, No. 2, 2007 Chemistry

Alexander Zaichenko1, Natalya Mitina1, Kateryna Rayevska1, Taras Skorohoda1,

Jan Zawadiak2, Danuta Gilner2, Volodymyr Lobaz1 and Volodymyr Novikov1

DESIGN OF POLYMERS OF BLOCK, COMB-LIKE AND HIGHLY

BRANCHED STRUCTURES WITH PEROXIDE-CONTAINING CHAINS
Lviv Polytechnic National University, 12 S. Bandera St., Lviv, 79013, Ukraine
1

zaichenk@polynet.lviv.ua
2
Silesian Technical University, 4 Krzywoustego St., Gliwice, Poland
janzaw@zeus.polsl.gliwice.pl
Received: May 18, 2007

Abstract. The tailored synthesis of telechelic 2. Experimental

oligoperoxides (TO), oligoperoxide metal complexes
(OMC) as well as the development of controlled radical
polymerization in aqueous and hydrocarbon media
initiated by them provides prospective approaches for
the obtaining block, comb-like and branched polymers
with the backbone and branches of various nature,
polarity, length and reactivity. The polymer-precursors
and final products were investigated by chemical, spectral
and rheological techniques. The novel peroxide-
containing copolymers were studied in the reactions of
in radical polymerization heterogeneous and homo-
geneous media.
Key words: peroxide telogen, coordinating oligoperoxide
metal complexes, controlled radical polymerization, block
copolymer, comb-like copolymer, branched polymers.
1. Introduction
Until now the technique of radical polymerization
for obtaining highly branched functional
macromolecules is not prevailing in comparison with
the methods of polycondensation and polymer analogous
transformations [1-3]. This is caused firstly by the
indeterminancy of structure and chain length peculiar
to polymers derivable by radical polymerization
techniques. Since the synthesis of telechelic
oligoperoxides (TO) and oligoperoxide metal complexes
(OMC) with side peroxide fragments allows controlling
radical polymerization initiated by them [4, 5] it
provides the realistic and very promising approach for
the obtaining block, comb-like and branched polymers
with the backbone and branches of predictable chain
structure, length, polarity, and reactivity. The
development of the tailored synthesis of new surface-
active reactive block, graft and branched copolymers
with peroxide-containing chains is the aim of the work.
Monomers: Vinyl acetate (VA), acrylic acid (AA),
styrene (St), butyl acrylate (BA), N-vinyl pyrrolidone (N-
VP), 2-tertbutyl peroxy-5-methyl-1-hexene-3-yne (VEP)
were purified using vacuum distillation; glicydyl
methacrylate (GMA), Merck was used as obtained; maleic
anhydride (MAN) was purified using sublimation technique.
Telogens: 1-(1-tertbutylperoxy-1-methylethyl)-4-
isopropylbenzene (MP) was purified by vacuum distilla-
tion; 2-Isopropyl-6-(1-hydroperoxy-1-methylethyl)
naphthalene (MHP) was purified by recrystallization from
hexane (Oact= = 6.30 %, purity - 96%) [6].
Initiators: Oligoperoxide metal complexes (OMC)
were obtained by complexation reactions of VA-VEP-
MAN, VA-VEP-BA-MAN with copper chloride in methanol
solution under room temperature and mild stirring
(polymer: CuCl2 weight ratio is 1: 1) then precipitated with
distilled water, filtered and dried under vacuum; 2,2’-
Azobis(2methylpropionitryle) (AIBN), Merck was used
as obtained.
Solvents: Ethyl acetate, dioxane, toluene, methanol,
benzene were analytical grade and used without additional
purification.
Sample preparation
Synthesis
All polymerization reactions were performed in glass
dilatometers under argon to control reaction kinetics and
product yield. Synthesis conditions are given in discussion.
Obtained samples were twice reprecipitated from organic
solvents and dried under vacuum. Vinyl alcohol fragments
in polymer molecules were obtained by alkaline hydrolysis
of VA links in methanol solution.
Sample characterization
Content of peroxide-containing links. Contents of
VEP and MP links were calculated from the amount of
products of decomposition of peroxide groups detected
on Selmi Chrom-1 gas-liquid chromatograph according
to [7]. Content of MHP links was determined using
iodometric technique.
72 Alexander Zaichenko et al.

Surface tension of water-ammonia solutions of 3. Results and Discussion

polymers was measured with PPNL-1 device by the
technique of excessive pressure in the vesicle. 3.1. The synthesis of macroinitiators-
Rheology Intrinsic viscosity [ç] of polymer precursors for block copolymerization
solutions was measured with Bishoff viscosimeter, in
acetone, at 298K. In case of homopolymers viscosity- Macroinitiators – precursors for block copolyme-
average molecular weights were calculated using equation: rization were synthesized by telomerization of VA, AA,
[h] = KMa and referred [8] K and a values. St or their mixtures with BA, MAN in hydrocarbon
UV-visible spectrometry was performed with media with participation of the telogens (T) of the
SPECORD-40 (Germany). structures:
1
H NMR spectra were recorded on 300 MHz
Brucker device.

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Earlier [9] we have shown that only one terminal peroxide fragment of MP or MHP is included in the polymer
structure providing the availability of active radical-forming site in the molecule of polymer-precursor.
Table 1
The synthesis and characterization of polymers with terminal peroxide fragments
([AIBN] = 10×10-3 mole/l, 333Ê)

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The characteristics of the kinetics of polymerization
(Table 1) show that polymerization in the presence of
peroxide-containing chain transfer agents occurs with feasible
rate and yield and provides the obtaining telechelic oligomers.
It is evident that the rate of polymerization, TO chain length
and peroxide functionality are determined by the telogen nature
and amount in initial reaction system as well as by the reaction
conditions. One can see from the experimental data (Table
1) that MP and MHP are effective chain transfer agents
possessing weakly inhibitory action, which cause the
decrease of the polymerization rate values and lowering TO
molecular weight at increase of telogen concentration.
Moreover, the kinetic characteristics of the polymerization,
molecular weight and functionality of peroxide-containing
oligomers depend on the nature and composition of monomer
system.
The presence of the common absorption bands in
UV-spectra of peroxide-containing telogens and oligomers
with end MP or MHP fragments (Fig. 1, Fig. 2) confirms
the entering active telogen residua into TO structure.
 Design of Polymers of Block, Comb-Like and Highly Branched Structures... 73








H

H

 

  


 

   
  
QP 
QP 
Fig. 1. Electronic spectra 1 - MP, 2 – poly VA-MP; Fig. 2. Electronic spectra 1 - MHP, 2 - poly AA-MHP;
3 - poly VA-BA-MP 3 – poly VA-BA-MHP

 

 



K u



VP1P

 

 
H

D
D 

 

 

   

03 

0+3    

QP 
Fig. 3. Surface tension at cmc (1, 1a) and intrinsic Fig. 4. Electronic spectra of block-copolymers:
viscosity (2, 2a) of polymers VA-MA – MP (1, 2) 1 - MP, 2 – polyvinyl alcohol - St (Mn = 10000 g/mole;
and AA-MHP vs. MP or MHP content 3 – polyvinyl alcohol - BA (Mn = 8200 g/mole)

The entering hydrophobic terminal residuum in
oligomer molecule leads as well to enhancement of TO
surface activity (Fig. 3). The TO molecules form
micelle-like structures in water solutions and can
solubilize water insoluble liquids. The surface activity
measured at CMC witnesses the changing TO
hydrophilic-hydrophobic balance as a result of entering
MP or MHP fragment.
The availability of terminal peroxide-containing
group in TO molecule and its controlled solubility and
surface activity provide the possibility of obtaining various
block-copolymers by the techniques of solution or water
dispersion polymerization initiated by TO.
It is clear from the Table 2 representing the
characteristics of the synthesis and properties of obtained
block-copolymers that TO are active initiators of solution
polymerization of various monomer systems. The initial
polymer – initiators and resulting block-copolymers are
of a different solubility and can be separated by dilution
and precipitation in distinct solvents. The obtained block-
copolymers can be composed of blocks of different
polarity containing various functional fragments including
peroxide groups. The variation of the synthesis conditions,
nature and concentration of both initial TO-initiator and
monomer mixture provides the controlling block-
copolymer chain length, hydrophily and reactivity.
74 Alexander Zaichenko et al.

Table 2
The synthesis of block-copolymers and their characterization (358Ê, benzene, monomer:solvent 1:3)

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The structures of block-copolymers obtained by 3.2. The synthesis of macroinitiators-

such technique are proved by both the chemical, UV- precursors for graft copolymerization
spectral and NMR-spectral methods (Table 2, Fig. 4, 5).
Macroinitiators – precursors for graft copolymerization
were synthesized by copolymerization of VA with BA, MAN
or AA and unsaturated peroxide of a structure:



&+ &+
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 VEP





as monomer and chain transfer agent simultaneously in


hydrocarbon media and derived metal complexes on their
basis as referred [10]. Earlier we have shown [5] that
oligoperoxide metal complexes (OMC) are low temperature












macroinitiators of radical polymerization in hydrocarbon



SSP and water dispersion media providing controlled obtaining

graft copolymers of various backbone and side functional
chains including groups of peroxide functionality. Some
Fig. 5. NMR-spectra of initial
characteristics of OMC-precursors are presented in the
telogen MPH, (1), TO AA-MPH (2)
and poly AA – block – poly St copolymer (3)
Table 3.
 Design of Polymers of Block, Comb-Like and Highly Branched Structures... 75

Table 3
Characterization of OMC - precursors of graft- (co) polymerization
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It is evident from the Table 4 representing comb-like
copolymer characteristics that they contain various
functional groups including active ditertiary peroxide ones.
One can see that obtained copolymers can be of controlled
surface activity, solubility and reactivity, especially in the
secondary processes of radical polymerization (Fig. 4). It
is evident that grafting hydrophobic polystyrene chains to
molecules of OMC-initiator leads to the enhancement of the
product surface activity in water-alkaline medium, thereby
they can be used as radical-forming surfactants for the
synthesis of branched polymers and colloidal particles with
pre-definite shell functionality and reactivity.
The coincidence of the characteristic absorption
bands peculiar to Cu2+ – containing fragments in the
molecules of OMC and derived comb-like copolymer
testifies the structural entering the OMC residual fragments
into the molecule of graft-copolymer obtained as a result
of polymerization initiated by OMC-precursor (Fig. 6).

Table 4
The synthesis and characterization of comb-like copolymers
(358Ê, benzene, monomer: solvent=1:3)
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Fig. 6. Surface tension isotherms of OMC-precursor (1) Fig. 7. UV - visible spectra of OMC (1)
and comb-like OMC-graft-poly St (2) on its basis and OMC-graft-poly St (2) on its basis
in water-ammonium solution
76 Alexander Zaichenko et al.
3.3. Macroinitiators - precursors
for obtaining branched copolymers
As it is clear from the scheme presented below
block- and comb-like copolymers containing radical-
forming ditertiary peroxide fragments in the chains are
prospective macroinitiators-precursors providing
obtaining branched polymers. They initiate radical
polymerization in organic solutions in a wide
temperature range causing the formation of branched
copolymers with new branches of tailored length,
functionality and reactivity (Table 5, Fig. 8, 9).
The rheological characteristics of polymer products
obtained at polymerization initiated by metal complexes
3UHFXUVRUJUDIWFRSRO\PHU








 
    
WPLQ
Fig. 8. St conversion vs. time polymerization initiated
by comb-like copolymer OMC (VA-VEP-MA)-graft- poly
(BA-VEP-AA) (1) and OMC on its basis (2) (323K,
benzene, [I] = 10%, St: benzene 1:3)
on the basis of peroxide-containing macroinitiators of
different degree of branching witness the formation in
solution of new compact polymer structures peculiar to
branched copolymers (Table 5). The changing structure
and properties of obtained branched copolymers as a
result of the multi-grade branching is justified as well by
the appearance of the tailored adsorb ability. The
combination of hydrophobic and hydrophilic peroxide-
containing branches of different length in highly
branched copolymers provides, their possibility to
significant water absorption (Fig. 9). It is evident from
the Fig. 9 that water absorption power of copolymers
increases with the enhancement of the number of
branched copolymer generations.

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 WK 
Fig. 9. Content of Í2Î absorbed in composite
on the basis of isoprene rubber filled with the copolymers
(1:1 weight): 1 – poly (VAlc-VEP-MA=20:47:33),
2 – poly (VAlc-VEP-MA) - graft-poly (BA-VEP-
AA=15:15:70); 3 – poly (VAlc-VEP-MA) - graft-poly
(BA-VEP-AA)- graft-poly (BA-AA=10:90);
4 – poly (VAlc-VEP-MA) - graft-poly (BA-VEP-AA)-
graft-poly (BA-AA=20:80) vs. time
 Design of Polymers of Block, Comb-Like and Highly Branched Structures... 77

Table 5
Rheological characteristics ([h], l/g) of OMC, copolymer OMC –graft-P1
and derived copolymer OMC –graft-P1-graft – P2
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78 Alexander Zaichenko et al.
4. Conclusions
The principal possibility of using the peroxide
monomer or telogen as well as surface-active
oligoperoxides on their basis for tailored design of reactive
macromolecules of block, comb-like and branched
structures with peroxide-containing chains of various
nature, hydrophily and reactivity was shown.
The kinetic study of new copolymer properties
displayed that they are surface-active substances with
controlled solubility, rheological characteristics, surface
activity, and capability to radical forming in a wide
temperature range.
The developed novel functional polymers are of a
great interest for biomedical application and proposed
synthesis techniques is accessible for their obtaining and
controlled design.
Acknowledgement: The authors express the
thanks to Science and Technology Center in Ukraine
for financial support of this work, Project # 1930
and 4140.
References
[1] Tomalia D.A., Naylov A.M. and Goddard W.A.: Angew.
Chem. Inter.Ed.Eng., 1990, 29, 138.
[2] Issberner J., Moors R. and Votle F.: Angew. Chem. Inter.
Ed. Eng., 1994, 33, 2413.
[3] Newkome G.R., Mishra A. and Moorefield C.N.: J. Org.
Chem., 2002, 67, 3957.
[4] Zaichenko A., Mitina N., Shevchuk O., Hevus O., Kurysko
T., Bukartyk N. and Voronov S.: Macromol. Symp. (React.
Pol.), 2001, 164, 25.
[5] Zaichenko A., Mitina N., Kovbuz M., Artym I. and Voronov
S.: Macromol. Symp. (React. Pol.). 2001, 164, 47.
[6] Stec Z., Zawadiak J.: Polish Journal of applied chemistry,
1998, XLII (3-4), 237.
[7] Vasilev V.P.: Homolytic decay of alkenealkyl peroxide
monomer and derived polymers. PhD thesis 02.00.03, 02.00.04.-
Lviv, 1990, 156.
[8] Toroptseva A.M., Belogorodskaya K.V. and Bondarenko
V.M.: Laboratornyj praktikum po khimii I technologii
vysokomolekulyarnyh soedinenij. Leningrad, Khimia, 1972.
[9] Samaryk V.Ya., Varvarenko S.M., Zaichenko O.S., Nosova
N.G., Roiter Yu.V., Mitina N.Ye., Hevus O.I. and Tarnavchyk
I. T.: Dopovidi NAN Ukrainy, 2002, 12, 118.
[10] Zaichenko A., Mitina N., Kovbuz M., Artym I. and
Voronov S.: J. Polym. Sci., 2000, À38, 516.
ÑÈÍÒÅÇ ÏÅÐÎÊÑÈÄÂ̲ÑÍÈÕ ÏÎ˲ÌÅв ÁËÎÊ-,
ÃÐÅÁÅÍÅ- ÏÎIJÁÍί ÒÀ ÐÎÇÃÀËÓÆÅÍί ÑÒÐÓÊÒÓÐ
Àíîòàö³ÿ. Ö³ëåñïðÿìîâàíèé ñèíòåç òåëåõåëàòíèõ
îë³ãîïåðîêñèä³â (ÒÎ), ôóíêö³îíàëüíèõ îë³ãîïåðîêñèäíèõ
ìåòàëîêîìïëåêñ³â (ÎÌÊ) òà äîñë³äæåííÿ êîíòðîëüîâàíî¿
ðàäèêàëüíî¿ ïîë³ìåðèçàö³¿ ó âîäíîìó ³ îðãàí³÷íîìó ñåðåäîâèùàõ
çà ¿õ ó÷àñòþ îáóìîâëþº ïåðñïåêòèâí³ ï³äõîäè äëÿ îäåðæàííÿ
áëîê-, ãðåáåíåïîä³áíèõ ³ ðîçãàëóæåíèõ ïîë³ìåð³â ç îñíîâíèì
òà áîêîâèìè ëàíöþãàìè ð³çíî¿ ïðèðîäè, ïîëÿðíîñò³, äîâæèíè
³ ðåàêö³éíî¿ çäàòíîñò³. Âèõ³äí³ òà ê³íöåâ³ ïðîäóêòè áóëè
äîñë³äæåí³ õ³ì³÷íèìè, ñïåêòðàëüíèìè òà ðåîëîã³÷íèìè
ìåòîäàìè. Íîâ³ êîïîë³ìåðè, ùî ì³ñòÿòü ïåðîêñèäí³ ãðóïè,
äîñë³äæóâàëè â ðåàêö³ÿõ ðàäèêàëüíî¿ ïîë³ìåðèçàö³¿ â
ãîìîãåííîìó òà ãåòåðîãåííîìó ñåðåäîâèùàõ.
Êëþ÷îâ³ ñëîâà: ïåðîêñèäíèé òåëîãåí, êîîðäèíàö³éíèé
îë³ãîïåðîêñèäíèé ìåòàëîêîìïëåêñ, êîíòðîëüîâàíà ðàäèêàëüíà
ïîë³ìåðèçàö³ÿ, áëîê-êîïîë³ìåð, ãðåáåíå-ïîä³áíèé êîïîë³ìåð,
ðîçãàëóæåí³ êîïîë³ìåðè.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 1, No. 2, 2007
Yuliya Voloshyna, Lyubov Patrylak, Ivan Manza and Angela Yakovenko
INFLUENCE OF ZEOLITE CRYSTALS EXTERNAL SURFACE
MODIFICATION ON TOLUENE PARA- DISPROPORTIONATION
SELECTIVITY
Institute of Bioorganic Chemistry and Petrochemistry, Ukrainian National Academy of Sciences,
50 Kharkivske chausee, 02160 Kyiv, Ukraine.
vljjj@mail.ru
Received: May 07, 2007
Abstract. On the basis of HZSM-5 a series of catalysts
with the deactivated external surface have been prepared
by extracting aluminium atoms from zeolite crystals or
by covering this zeolite’s surface with the tetraethoxysilane
thermal destruction products. It has been discovered that
the external surface deactivation is not the main factor of
the para-selectivity increasing in the toluene to benzene
and p-xylene disproportionation reaction. It is decreasing
of the diffusion of o- and p-xylene from the catalyst pores
on the external surface of zeolite crystals that seems to be
the determinant.
Key words: Toluene disproportionation, HZSM-5 zeolite
catalysts, para-selectivity, external acid sites, external
surface deactivation, diffusion.
1. Introduction
Today the toluene disproportionation is one of the
important ways of producing benzene and particularly
p-xylene. Two main methods of improving the
disproportionation para-selectivity on zeolites are known:
reduction of catalyst diffusive-kinetic characteristics to
enlarge the residence time of m- and o-xylenes in the
catalyst pores, thereby promoting their transformation into
para-isomer [1, 2] and deactivation of external surface
acid sites to prevent the undesirable isomerization of p-
xylene to m- and o-isomers [3, 4]. There is no generally
accepted opinion concerning the priority of one of these
two approaches. Industrial processes involve, as a rule,
the techniques of the pre-coking or surface silica deposition
to increase the most desirable p-isomer content in xylene
mixture. However the question is open where the formed
coke species are located [4, 5]. Both of the methods have
shortcomings [6]: intensification of cracking processes
and partial loss of catalyst activity, respectively.
We have not found the reports about deactivation
of the catalysts external surface by removing active sites.
The aim of this work is synthesis of HZSM-5
samples with the deactivated in different ways zeolite
Chemistry
crystals external surface, and investigating of their
properties in the toluene to benzene and xylenes
disproportionation.
2. Experimental
To attain the above aim we have used 2, 4, 6-trinit-
rophenol (TNPh, or picric acid), tetraethoxysilane (TEOS),
and silicon tetrachloride, the last as a vapour.
ZSM-5 (SiO2/Al2O3=41) H-form has been obtained
by the ion exchange of parent Na+ cations for NH4+ cations
with further calcination (sample 1).
Dealumination was performed by treating the initial
zeolite samples with correspondent amount of aqueous
(samples 2, 3, 5, 6) or spirituous (ethanol) (sample 4)
solutions of TNPh at 373 K (water bath) or ambient
temperature, respectively.
Modifying HZSM-5 by thermo destruction of
tetraethoxysilane has been realized in the air-dry (sample 7)
or dehydrated (sample 8) states, the samples being added to
the definite volume of TEOS hexane solution (solid to liquid
phase ratio 1:3). The suspension has been stirred for 15 min.
Then hexane has been vaporized, and the samples have been
calcined at 773-823 K for 3 h. The temperature was being
raised with the speed of 3 degrees per min. SiO2 deposits
have been determined to be as 6,5 and 2,3 wt.% for samples
7 and 8 correspondingly, sample 7 being double modified.
Catalyst 9 was synthesized by treating ZSM-5 with
SiCl4 vapour in autoclave under static conditions at 623 K
with further washing and obtaining H-form under the
above mentioned conditions.
The catalytic properties of the samples (100 mg of
each) have been investigated at 773 K in micro pulse set-
up assembled on the base of “TSVET -500” chromato-
graph (capillary column 50 mm in length with 0.5 mm
inner diameter, tvin-60 as the stationary phase, flame
ionizing detector) using hydrogen as carrier gas (10-120
cm3/min) under low surplus pressure. The toluene pulse
volume was 2 ml.
80 Yuliya Voloshyna et al.

3. Results extraframework-Al-free sample 6 lets us suppose that

3.1. Acid treatment of the ZSM-5
Due to having molecules of large size, theoretically
picric acid can extract aluminium atoms from the zeolite
external surface only. Furthermore, rather external
dealumination is known [7] to take place when sodium
form of a mordenite is subjected to acid treatment.
Therefore in addition to its H-form Na-form of ZSM-5
was used as catalyst basis.
The Table summarises the aluminium elimination
data from the samples 2-6. The content of external acid
sites has been taken as equal to 0.023 mmol/g [8].
Table
Dealumination of ZSM-5 zeolites by aqua (aq)
and ethanol (EtOH) solutions of trinitrophenol
$PRXQWRI
,QLWLDOIRUP $PRXQWRIDOXPLQLXP
 WULQLWURSKHQRO
RI]HROLWH H[WUDFWHGPPROJ
PPROJ
 +\GURJHQ  
dealumination of zeolite framework by the picric acid still
takes place, and acid molecules can penetrate the deeper
layers of zeolite crystals extracting the aluminium atoms
also from the sites near the pores entrances as well.
3.2. Catalytic testing
The catalytic properties of the samples synthesized,
in particular their para-selectivity (S p), have been
investigated in their dependence on the of carrier gas flow
rate that effects the residence time of both reactive and
product molecules within the catalyst cavities. We were
interested to study the para-selectivity of the samples and
their dependence on the preparation method at small
residence time of both initial toluene and conversion
products on the catalyst bed. Such testing method prevents
further conversion of the primary reaction product,
especially on the external surface of zeolite crystals, which
excludes the undesired process selectivity decrease due
to the above mentioned possible isomerization of p-xylene
to ortho- and metha-isomers.
 +\GURJHQ DT  The data obtained (Figure) evidence that the
preparation method is of great importance from the
 6RGLXP DT  standpoint of para-selectivity. The curves 4, 5, 6 for acid
 +\GURJHQ (W2+ 
 +\GURJHQ DT 
 6RGLXP DT 
The data obtained for the sample 2 show the amount
of aluminium extracted to be greater than the number of
external Al atoms. There are two possible reasons for this
fact. The first one is extracting by the acid the extra
framework aluminium generated during the H-form
obtaining: only such aluminium or total, including that of
external surface. The second reason is the ability of TNPh
to dealuminate not only the external surface, as it may be
expected due to comparably large picrate-anions sizes,
but the internal surface as well.
Absence of Al in the filtrate from the sample 3
(NaZSM-5) seems to support the first assumption (Table).
However, on the other hand, the absence of NaZSM-5 Figure. Dependences of selectivity for p-xylene (Sp)
dealumination may be connected with the acting acid on carrier gas (W) flow rate for different catalysts
concentration decrease, as in the Na-zeolites the (curve numbers coincide with the sample numbers
substitution of Na cations for acid protons occurs prior in the text and in the Table)
to the Al extraction from the zeolite structure [9].
Therefore we have increased the concentration of acid treated zeolites are situated not far from the curve of the
solution (samples 4-6), additionally using ethanol instead initial sample 1: Sp value does not exceed 40 % at the flow
of water in case of sample 4 synthesis. rate of the carrier gas up to 120 ml/min. The dependences
In spite of more concentrated ethanol solution for TEOS modified samples 7 and 8 start near the
(sample 4) we have failed to eliminate more aluminium unmodified sample curve 1, shifting subsequently upwards
atoms from the zeolite as compared to water solution to 50-60 % values. As was mentioned above, sample 7,
conditions (samples 2, 3) which might be due to a small unlike sample 8, has not been dehydrated before TEOS
degree of TNPh dissociation in ethanol resulting from lower impregnation. Finally, sample 9 on the base of zeolite treated
dielectric permeability of the latter. However increase in by SiCl 4 demonstrates the highest para-selectivity,
the amount of eliminated Al along with increased acid originating from more than 60 % and reaching the highest
quantity in the cases of sample 5 and especially of value of about 90 % at carrier gas rate of 90 ml/min.
 Influence of Zeolite Crystals External Surface Modification...
4. Discussion
In spite of the expectations, the deactivation of
external surface of the zeolites has not only failed to improve
their para-selectivity but even somewhat decreased it. On
the base of the chemical analysis results (Table) we arrived
at a conclusion about the extraction of aluminium atoms
from the sites near the pore entrances, which leads to the
pore entrances diameters increasing. In consequence we
have succeeded in external surface deactivating of samples
2, 4-6 when simultaneously increasing the ability of reaction
products to diffuse from the zeolite channels, i.e. increasing
the departure of the undesired o- and m-xylenes on the
external surface of zeolite crystals.
On the other hand, we believe that during the
HZSM-5 modification by TEOS, not only external surface
inactivation occurs but also partial blocking of pore
openings by the products of TEOS destruction takes place.
The latter seems to be true especially for sample 8, in
which SiO 2 cover might expend towards the pores
mouths, reinforcing the molecular sieve effect, as zeolite
channels of this sample were preliminarily emptied from
water molecules. In case of sample 9, similarly to SiCl4 -
treated Y-type zeolite [10, 11], some amount of
extraframework species have probably formed in the
channels of the catalyst thus hindering free movement of
the molecules produced.
That is why the catalysts selectivity seems to be
strongly dependent on the extent of the steric hindrances
to the migration of more bulky o- and m-xylene isomers
within the crystals of zeolite basis. One can assume that
the absence of the sites for the secondary p-xylene
isomerization on the external surface of a catalyst seems
to be of some positive influence on the p-selectivity only
for sample 4 with the smallest rate of the acid modification
and the highest carrier gas rate (Figure). At the same time
the larger the pores’ openings the lower para-selectivity
is observed regardless of the external surface deactivation
(samples 5, 6). On the contrary, inhibition of the diffusion
of more bulky isomers from the zeolite channels increases
para-selectivity of samples 7, 8, and especially 9 in the
whole carrier gas rate diapason.
Therefore, under applied micro pulse reaction
conditions, deactivation of external surface by removing
the active sites using picric acid does not enhance the
selectivity of toluene disproportionation process. The
effect is levelled down by zeolite pore entrances
enlargement. The pore size restricting plays the dominant
role in attaining the high para-selectivity in toluene
disproportionation reaction. Taking into account that even
the smallest applied carrier gas rate cannot decrease para-
selectivity of sample 9 below 60 % (that is twice as much
as the value for unmodified zeolite), the tendency observed
may remain valid for the increased residence time of all
81
the components on the catalyst bed. These aspects of
disproportionation require additional investigation. What
can be stated definitely is that the highest yields of p-
xylene can be achieved by combining the lowest acidity
of the external surface of zeolite crystals and maximum
decreased diffusivity of zeolites.
Regarding the positive influence of the preliminarily
zeolite catalyst coking upon the disproportionation results,
mentioned in the introductory part of the paper, such an
influence can be caused not only by narrowing the
entrances to zeolite cavities by coke, but similarly to the
TEOS action, deactivating the external surface of zeolite
crystals by blocking external surface acid centres.
References
[1] Hibino T., Niwa M. and Murakami Yu.: J. Catal., 1991, 128, 551.
[2] Kaeding W.W., Young L.B. and Chu Ch.-Ch.: J. Catal.,
1984, 89, 267.
[3] Zhu Zh., Chen Q., Xie Z., Yang W., Kong D. and Li C.: J.
Mol. Catal. A: Chem., 2006, 248, 152.
[4] Uguina M.A., Serrano D.P., Van Grieken R. and Venes S.:
Appl. Catal., A, 1993, 99, 97.
[5] Chen W.H., Jong S.J., Pradhan A., Lee T.Y., Wang I., Tsai
T.-C. and Liu S.-B.: J. Chin. Chem. Soc., 1996, 43, 305.
[6] Tsai T.-C., Liu S.-B. and Wang I.: Appl. Catal., A, 1999,
181, 355.
[7] Mishin I.V. and Beyer H.K.: Kinetika i kataliz, 1998, 39, 68
[8] Bobik V.V., Voloshina Yu.G. and Bobonich F.M.: Theor.
Exp. Chem., 2004, 40, 320.
[9] Baran B.A., Belenkaya I.M.and Dubinin M.M.: Russ.
Chem. Bull., 1973, 22, 1662.
[10] Anderson M.W. and Klinowski J.: J. Chem. Soc., Faraday
Trans. 1, 1986, 82, 1449.
[11] Vereshchagina T.A., Kirik S.D., Vereshchagin S.N., Rubailo
A.I., Selina V.P. and Anshits A.G.: Russ. Chem. Bull., 1990, 39, 861.
ÂÏËÈ ÌÎÄÈÔ²ÊÓÂÀÍÍß ÇÎÂͲØÍÜί ÏÎÂÅÐÕͲ
ÖÅÎ˲ÒÍÈÕ ÊÐÈÑÒÀ˲ ÍÀ ÏÀÐÀ-ÑÅËÅÊÒÈÂͲÑÒÜ
ÄÈÑÏÐÎÏÎÐÖ²ÎÍÓÂÀÍÍß ÒÎËÓÎËÓ
Àíîòàö³ÿ. Íà îñíîâ³ öåîë³òó HZSM-5 ïðèãîòîâàíî
ñåð³þ êàòàë³çàòîð³â ç äåçàêòèâîâàíîþ çîâí³øíüîþ ïîâåðõíåþ
øëÿõîì âèëó÷åííÿ àòîì³â àëþì³í³þ ç öåîë³òíèõ êðèñòàë³â àáî
ïîêðèòòÿì ö³º¿ ïîâåðõí³ ïðîäóêòàìè òåðì³÷íîãî ðîçêëàäó
òåòðàåòîêñèñèëàíó. Çíàéäåíî, ùî äåçàêòèâàö³ÿ çîâí³øíüî¿
ïîâåðõí³ íå º îñíîâíèì ôàêòîðîì çðîñòàííÿ ïàðà-
ñåëåêòèâíîñò³ â ðåàêö³¿ äèñïðîïîðö³îíóâàííÿ òîëóîëó äî
áåíçîëó é ï-êñèëîëó: òàêèì áà÷èòüñÿ ïîã³ðøåííÿ äèôó糿 î- ³
ì-êñèëîëó ³ç ïîð êàòàë³çàòîð³â íà çîâí³øíþ ïîâåðõíþ öåîë³òíèõ
êðèñòàë³â.
Êëþ÷îâ³ ñëîâà: òîëóîëó äèñïðîïîðö³îíóâàííÿ, HZSM-5
öåîë³òíèé êàòàë³çàòîð, ïàðà-ñåëåêòèâí³ñòü, çîâí³øíüî-
ïîâåðõíåâ³ êèñëîòí³ öåíòðè, äåçàêòèâàö³ÿ ïîâåðõí³, äèôóç³ÿ.
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 1, No. 2, 2007 Chemistry

Ananiy Kohut1, Roman. Fleychuk2, Orest Hevus2 and Stanislav Voronov2

MACROINITIATORS ON THE BASIS OF NEW PEROXIDE SURFACE

ACTIVE MONOMERS
1
Institute of Particle Technology, University of Erlangen-Nuremberg, Erlangen, Germany
2
Lviv Polytechnic National University, 12 Bandera Str., Lviv, 79013, Ukraine
fleychuk@polynet.lviv.ua

Received: March 27, 2007

Abstract. The surface active properties of new peroxide
maleic monomers were investigated. The regularities of
their copolymerization with styrene were studied. Peroxide
polymers containing ditertiary alkyl peroxide groups in
side substituents of backbone as the prospective high-
temperature free radical macroinitiators were synthesized.
Keywords: copolymerization, macromonomers, mono-
mers, peroxides, surfactants.
1. Introduction
The use of peroxide monomers in the reactions of
copolymerization permits the introduction of peroxide
groups into the macromolecule structure [1], which are
able to generate free radicals including macroradicals. That
is why, such polymers are able to initiate various radical
processes, e.g. graft polymerization, vulcanization,
structurizing. The utilization of peroxide macroinitiators
enables to synthesize polymers with complex molecular
architectures [2].The modification of diverse micro- and
macrosurfaces with peroxide macroinitiators allows to
design polymer nanolayers on these surfaces by the
initiation of radical polymerization of vinyl monomers from
them [2]. Specifically, it permits to obtain core-shell latex
particles as well as perform pigment surface modification
with the purpose of improving the dispersibility of pigment
particles. On the other hand, the formation of polymer
colloid systems by the reactions of copolymerization using
surface active monomers (surfmers) is known to be one
of the most convenient ways for their stabilization due to
the covalent tethering of surfactant onto latex particle
surface [3, 4]. These systems are stable with regard to
electrolytes as well as over wide pH and temperature
ranges. Polymer films with improved physical-chemical
and exploitational properties are formed on the basis of
the latexes obtained with surfmer utilization. A surfmer
molecule consists at least of three different parts:
polymerizable group, as a rule, a carbon-carbon double
bond, and of hydrophilic and oleophilic parts as a
conventional surfactant. The hydrophilic groups may be
both ionic (anionic or cationic) and non-ionic (e.g., an
oxyethylene chain of an appropriate chain length).
Hydrocarbon chains (alkyl chains, alkyl phenol chains) or
polypropylene oxide and polybutylene oxide chains are
used as hydrophobic molecule parts. Maleic surfmers are
known to have an additional advantage over other surface
active monomers. They do not undergo homopo-
lymerization [5] and this means that the surfmers do not
produce water soluble polymers (polysoaps) in the
aqueous phase [6]. However, they copolymerize with other
monomers. Maleic surfmer is covalently anchored onto
the surface of the polymer particles at the emulsion or
dispersion polymerization process and therefore it is not
practically incorporated into the polymer bulk.
This work is devoted to the study of surface active
properties and polymerization ability of non-ionic and
anionic peroxide monomers of the following structures:

2 2 2

2 22 2 22 2 22
2+ 2 62 1+(W 2 +
2 
2   2   2  

This kind of polymerizable surfactants seemed to be prospective for utilization in adhesives, coating formations etc.
84 Ananiy Kohut et al.

2. Experimental 3. Results and Discussion

2.1. Materials Surface tension of aqueous solution of the peroxide
surfmers 1-3 with the concentration, C % w/w, at 293K,
The monomers 1-3 were prepared by the methods are represented as semilogarithmic plots in Figure 1.
reported in previous papers listed below. In short, 3-tert-
butylperoxy-3-methylbutyl maleate 1 was synthesized by 
acylation of 3-tert-butylperoxy-3-methyl-1-butanol with
maleic anhydride [7]. The anionic monomer 2 was 
synthesized by the interaction of triethylammonium salt 
of monomaleate 1 with 1,3-propane sultone in dimethyl
formamide [8]. The acylation of poly(ethylene glycol) with 
molecular weight 300 g/mol by the chloroanhydride of 
hemiester 1 gives the non-ionic surface active peroxide


V
macromonomer 3 [8].
Styrene from Aldrich was distilled under reduced 
pressure just before utilization. The initiator, 2,2'-
azobis(isobutyronitrile), AIBN, from Merck was purified 
by recrystalization three times from anhydrous methanol.      
Methanol from Aldrich was dried by boiling with
OJ&
magnesium chips under reflux for 2-3 h and distilled.
Triethylamine from Merck was used as supplied. All Fig. 1. Semilogarithmic plots of surface tension s
experiments were performed with deionized water. of peroxide monomer solution vs. monomer concentration,
C % w/w, at 293K: (·) triethylammonium salt of surfmer 1;
(n) surfmer 2; (p) surfmer 3
2.2. Copolymerization in solution
Copolymerization of peroxide surfmer 3 with All the investigated peroxide monomers are
styrene was carried out at 333K in benzene solution. The obviously the surface active substances, since water
volume ratio solvent :  monomer mixture was of 5 : 1, surface tension decreases when the surfactants are added.
initiator – AIBN (2% w/w upon the monomer mixture). The monomers 2 and 3 are colloidal surfactants. The
The polymerization proceeded till monomer conversion surface tension decreases almost linearly with increasing
of 12-16%. The copolymerization was performed in concentrations of each of the surfmers and becomes
ampoules where benzene solution of maleate 3, styrene, constant above certain concentrations that evidently
and AIBN had been charged. The ampoule contents were corresponds to their critical micelle concentrations (cmc).
cooled to 195K, whereupon, vacuumized and charged with The monomer 1 forms true aqueous solutions up to the
argon five times in turn repeatedly. Then, ampoules were saturation. Above this concentration, it forms a separate
sealed. The polymers formed were purified by three phase.
precipitation cycles from benzene to hexane. The polymers The cmc values determined from an inflection point
were finally dried in vacuum at room temperature up to and the surface tensions at these values have been listed
constant weight and copolymer yields were calculated. in Table 1.
Copolymer composition was determined from elemental
analysis data and/or hydroxyl group content determined Table 1
as shown below. Critical micelle concentration (cmc)
and the surface tensions at the cmc
of the peroxide monomers
2.3. Measurements
The surface active characterization of maleic FPF VFPF
PRQRPHU
surfmers 1-3 was carried out by means of surface tension ZZ PROO P1P
measurements. These measurements were performed    
with a du Noüy ring tensiometer at 293K. A weighed    
portion of the peroxide surfmer 1 was dissolved in water
containing equimolar amount of triethylamine to measure
the surface tension.
Hydroxyl number of the copolymers prepared was The synthesized surfmers are able to copolymerize
determined by the method of acetylation with acetic with other monomers to form polymers with peroxide
anhydride catalyzed by perchloric acid in pyridine [9]. groups in side substituents of macrochain:
 Macroinitiators on the Basis of New Peroxide Surface Active Monomers 85

The copolymerization of maleic macromonomer 3 studied to determine the copolymerization constants. The
(M2) on the basis of PEG-300 with styrene (M1) has been results of the studies are presented in Table 2.

2 +
2 2 
2

2 22
[ \ 2 2
+
2  2 22
2

Table 2
Results of styrene (M1) copolymerization with the peroxide monomer 3 (M2)

(OHPHQWDOFRPSRVLWLRQRIFRSRO\PHUV +\GUR[\O
0RQRPHUPL[WXUH &RSRO\PHU
ZZ QXPEHURI
FRPSRVLWLRQ FRPSRVLWLRQ
FRSRO\PHUV
>0@>0@ & + 2 >P@>P@
PJ.2+J
   "   D
   "   D
     E
     E
     E
a)
determined from hydroxy group content.
b)
determined from elemental analysis data and hydroxy group content

The polymerization constants calculated according
to the Mayo-Lewis method using the composition equation
in the integrated form [10] are: r1 = 6.3 ± 0.2; r2 ® 0.
Figure 2 represents the composition diagram of the
copolymer.
One can see from Figure 2 that copolymers enriched
with styrene links in comparison with monomer mixture
compositions are formed during copolymerization of
macromonomer 3 with styrene in benzene solution.

 4. Conclusions
The investigated peroxide maleic monomers are

shown to possess surface active properties decreasing
surface tension at the air/water interface. The critical

micelle concentrations and the surface tensions at the
cmc have been determined for corresponding peroxide


 monomers. The peroxide surfmers were shown to be

able to copolymerize with traditional monomers retaining
 their peroxide group. As a result, prepared copolymers
contain –Î:Ζ groups in side substituents of skeleton
 macrochain that are able to initiate free radical processes:
     
graft copolymerization; vulcanization; structurizing etc.
>0@
The regularities of copolymerization of surface active
monomers with styrene have been studied and the
Fig. 2. The composition curve of the copolymer
copolymerization constants were determined. The
of styrene (M1) with the surface active peroxide
macromonomer 3 (M2) addition of poly(ethylene glycol) based maleic macro-
monomer to its own radical link is impossible during the
86 Ananiy Kohut et al.
copolymerization with styrene because of steric factors.
That is why styrene only is added to the maleate radical
as it is indicated by the copolymerization r2 value. The
monomers studied possess the surface active properties
and may be utilized as polymerizable emulsifiers to
perform the processes of emulsion polymerization of
conventional vinyl monomers (styrene, acrylates,
methacrylates etc.).
References
[1] Voronov S., Tokarev V., Oduola K., et.al.: J. Appl. Polym.
Sci., 2000, 76, 1217.
[2] Voronov S., Tokarev V., Datsyuk V., et.al.: J. Appl. Polym.
Sci., 2000, 76, 1228.
[3] Guyot A. and Tauer K.: Adv. Polym. Sci., 1994, 111, 43.
[4] Capek I.: Adv. Colloid Interface Sci., 2000, 88, 295.
[5] Busfield W. K., Jenkins I. D. and Heiland K.: Eur. Polym. J.,
1994, 30, 1259.
[6] Guillaume J. L., Pichot C. and Guillot J.: J. Polym. Sci., Part
A: Polym. Chem., 1990, 28, 137.
[7] Fleychuk R.I., Hevus O.I. and Voronov S.A.: Russ. J. Org.
Chem., 2003, 39 (12), 1799.
[8] Kohut A.M., Fleychuk R.I., Hevus O.I. and Voronov S.A.:
11th Internarional Conference on Chemistry of Organic and
Elementorganic Peroxides, 2003, 238.
[9] Siggia S. and Hanna J.G.: Quantitative Organic Analysis
via Functional Groups. New York, J. Wiley & Sons, 1979.
[10] Alfrey T., Bohrer J. J. and Mark H.: Copolymerization.
New York, J. Wiley & Sons, 1952.
ÌÀÊÐβͲֲÀÒÎÐÈ ÍÀ ÎÑÍβ ÍÎÂÈÕ
ÏÅÐÎÊÑÈÄÍÈÕ ÏÎÂÅÐÕÍÅÂÎ-ÀÊÒÈÂÍÈÕ
ÌÎÍÎÌÅвÂ
Àíîòàö³ÿ. Äîñë³äæåíî ïîâåðõíåâî-àêòèâí³
âëàñòèâîñò³ íîâèõ ïåðîêñèäíèõ ìàëå¿íàòíèõ ìîíîìåð³â.
Âèâ÷åíî çàêîíîì³ðíîñò³ ¿õ êîïîë³ìåðèçàö³¿ ç³ ñòèðåíîì ³
îäåðæàíî ïåðîêñèäâì³ñí³ ïîë³ìåðè, ÿê³ ì³ñòÿòü äèòðåòèíí³
àëê³ëüí³ ïåðîêñèäí³ ãðóïè â áîêîâèõ â³äãàëóæåííÿõ îñíîâíîãî
ìàêðîëàíöþãà – ïåðñïåêòèâí³ âèñîêîòåìïåðàòóðí³
ìàêðî³í³ö³àòîðè â³ëüíîðàäèêàëüíèõ ïðîöåñ³â.
Êëþ÷îâ³ ñëîâà: êîïîë³ìåðèçàö³ÿ, ìàêðîìîíîìåðè,
ìîíîìåðè, ïåðîêñèäè, ïîâåðõíåâî-àêòèâí³ ðå÷îâèíè.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 1, No. 2, 2007
Oleg Suberlyak and Volodymyr Skorokhoda
THE PECULIARITIES OF THE POLYVINYLPYRROLIDONE
COPOLYMERS SYNTHESIS FOR CONTACT LENSES
Lviv Polytechnic National University, Lviv, Ukraine
12, St.Bandera st., Lviv, 79013, Ukraine.
suberlak@polynet.lviv.ua
Received: April 18, 2007
Abstract. The research results of the hydrogels synthesis
rules on the basis of 2-hydroxyethylmethacrylate-
polyvinylpyrrolidone copolymers and effective ways of
adjusting of their proper­ties are given. Synthesized
copolymers appeared to be effective materials for
production of hydrophilic contact lenses.
Key words: hydrogel, polyvinylpyrrolidone, 2-hydro-
xyethylmethacrylate, contact lens.
1. Introduction
The intensive development of polymeric chemistry
and technology has resulted in wide introduction of
polymers in various areas of human activity, the special
interest among which represents the use of polymers in
medicine. At the early stages of biomedical polymers
development they were only substitutes of already known
polymers, later - as medicines, in the production of
instrumentation, stomatological instruments and artificial
organs of a human body. It should be noted, that the need
for such polymers is huge and is growing every year. So,
according to the data given by Prof. Atsymi Êàdzyhiko,
only in 2000, 150 thousand people of the globe needed
synthetic bones and joints, 2.5 million required blood
vessels, about 1 million people was in need of heart valves,
1.5 million – lungs, more than 1 million – kidneys.
However, life puts forward the more and more difficult
demands for polymeric materials that is why one of basic
directions, the polymeric science is developing now, is
the creation of such material system, which can completely
reproduce biological functions of a living organism.
The basic demands to synthetic organs are absolute
harmlessness for an organism, absence of cancerogenic
or allergic influence, stability of properties in time etc.
Besides, depending on specificity of that or other synthetic
Chemistry
organ, the material should also meet many other specific
requirements.
Besides mentioned above artificial organs, the
mankind is in great need of ophthalmologic implants –
intraocular, treating and correctional contact lenses. The
contact lenses are made in two modifications – solid
and soft. Their well-known advantage is hyper
permeability for an eye-water liquid and oxygen, the
property which appreciably reduces a discomfort of
lenses at use. In their turn, the soft contact lenses are
made either from hydrogels, or from silicones. The
silicone lenses have a hyper permeability for oxygen,
but they moisten badly and are impenetrable for an eye-
water liquid and are rather inconvenient for long using.
Investigations carried out in the trend of the creation
of long usage contact lenses are directed on the
development of materials, which should have a necessary
permeability for oxygen and eye-water liquid, as well as
provide high optical and mechanical properties at minimum
thickness and mass of a lens.
2. Results and Discussion
The Department of Chemical Technology and
Processing of Plastics of Lviv Polytechnic National
University has been carrying out investigations in the
field of synthesis and application of medical polymers,
including ophthalmologic ones, for more than 25 years.
Mainly, these investigations are directed on the synthesis
of new and modification of existing polymers. After the
long approbation period, polyvinylpyrrolidone (PVP) has
been chosen as the base starting product. Uniqueness of
PVP properties and its application are caused by its
structure and physical-chemical properties – the presence
of carbamatic group promotes high selective – sorption
properties, complex formation with iodine and other
inorganic and organic compounds, formation of and ionic
form of macromolecules in an aqueous medium [1]:
88 Oleg Suberlyak et al.

+2+
&+
& + &+
&  &+
&+ & 
&+ &+
& + &+
& 
1 1 1
+& & 2 +& & 2 +& & 2+ 2+
+& & 
&+ +& & 
&+ +& & 
&+

Besides, PVP is non-toxic and biologically compatible,
and it is successfully applied in medicine as a substitute of a
blood plasma. All this allows speaking about high functional
activity which will be shown by polymers and PVP polymers
including their contact with organism tissues.
The synthesis of PVP copolymers is developing in
two directions: in the first statistical copolymers of N-
vinylpyrrolidone with hydrophylic or hydrophobic mono-
mers (as a rule, acrylic) are received; in the second –
attached copolymers received on the basis of PVP
containing monomer compositions. In most cases these
&+  &
copolymers are rarely structured and swell to some extent
in water and organic solvents. According to their
properties, block and graft copolymers are similar, but as
for adaptability to manufacture polymer – monomer
compositions and attached copolymers are more attractive.
When using PVP-monomer reaction mixtures for the
synthesis of copolymers positive effect of the complex
formation with charge transfer (CCT) between monomer
(2- hydroxyethylmethacrylate (HEMA)) and polymeric
matrix was fixed [2]:
& 
&+ 2
& &++ Q & &
G
1 & 
&+ 2 & 
&+ &  2+
&+
2 & & 
&+
+& & 
&+
It plays a role of initiating system even without case initiation occurs according to the following
traditional peroxide initiators or N-compounds. In this scheme:

5 5
G

 
 &+ &+  &+  &  &+ &+  &+ &
& 2 1 & 2
1 G
& 2 2 5 & 2 2 5

5
 

 &+ &  &+ &
1 & 2
& 2 2 5

As the result, the formation of various finished effect was found out. It consists in the interconnection
products (homo- and graft (co)polymers) is possible. between constant of complex formation K C and
By means of polymerization research of widely structural parameters of copolymer grid and their
known HEMA in a composition with PVP, another CCT properties (Table 1).
Table 1
Dependence of PVP inoculation efficiency (f) and molecular weight of a grid
internodal fragment (Ìf) on a constant complexformation (KC ) in the system PVP-HEMA-dissolvent
  393FRQWHQWLQ
&GP PROH INJPROH I
FRSRO\PHUV
    
    
    
 a   

 The Pecularities of the Polyvinylpyrrolidone... 89

By means of those two revealed effects, we have subjected to essential morphological changes because of
developed ways of regulated synthesis of PVP copolymers physical transferring from glass figurative in highly elastic
with HEMA and dimethacrylate, which are characterized by condition. This makes possible for them to gain new
high sorption (Table 2) and selective diffusive properties physical properties and reach high compatibility with
(Table 4). Thus, it should be noted, that owing to a sorption organism tissues.
of a considerable quantity of water, most of them are
Table 2
Sorption properties of synthesized copolymers
6RUSWLRQRI
6RUSWLRQRI
& SRO\PHU (TXLOLEULXPZDWHUFRQWHQW KHSDULQ
S$6$   JJ
  XP  
SRO\+(    
393JUDIWSRO\+(0$ «  «  « 
SRO\ *     
393JUDIWSRO\ *  «   

Notes: * p-aminosalicylic acid

** TGM-3 - triethyleneglycoldimethacrylate

It should be noted, that during water sorption optical
properties of copolymers change differently depending on
structure. The conditions of copolymers synthesis and their
compositions have been defined, which are characterized
during hydration by stability of optical properties. This
enables to utilize them as starting materials for optical
correctional contact lenses. At the same time, large attention
was attached to the dependence of physical-mechanical
characteristics of the obtained materials on synthesis
conditions and copolymers composition (Table 3).

Table 3
Physical-mechanical properties of polymers in a hydrated condition
&RPSRVLWLRQFRQWHQWIRUK\GURJHOV\QWKHVLVPDVVS V H

+  393 *  3  
     
     
     
     
     
     
     
Note: s - tensile strength, e - relative elongation under rupture
Table 4
Sorption-diffusion properties of (co)polymers
 &RPSRVLWLRQFRQWHQWIRUK\GURJHO  :DWHUSHUPHDELOLW\ &RHIILFLHQWRISHUPHDELOLW\
 V\QWKHVLVPDVVS : ˜ PROH˜P˜K
 +  393   '  P˜P˜K 1D&O 8UHD 6DFFKDURVH
         
         
         
         
         

         

         
         
         
Notes: AD – aprotic dissolvent, W- water conent. coefficient of permeability of light for polymers
of composition 1-5,8,9 – 90…96 %.
* – opaque polymers
90 Oleg Suberlyak et al.
The application bifunctional oligomer products of
a type TGM-3 allows to increase essentially hardness of
hydrogels, however, in such a way the elasticity of
materials is reduced, that is caused by considerable
influence of TGM-3 on the copolymers grid density.
The physical-mechanical properties of copolymers
in equilibrium - swollen a state can change within a wide
range and the task of research was to define optically
transparent compositions, which should provide necessary
hardness and elasticity of materials. Thus the opportunity
of obtaining materials with varying hardness and elasticity
which are characterized by varying equilibrium water
content or identical water content was found out.
At the same time, the synthesized copolymers differ
not only by high sorption properties, but also by selective
– diffusive properties during a dialysis of aqueous solutions
(Table 4).
It is necessary to note, that the change of the
structure and composition of copolymers may considerably
influence the size of refraction index n D. This was
consequently used for optimization of copolymers
composition for contact lenses. It allowed receiving
correctional soft contact lenses [3] with the following
operational properties (Table 5).
Table 5
The characteristics of a polymeric material
for soft contact lenses
3DUDPHWHU
 3URSHUWLHVLQK\GUDWHGFRQGLWLRQ
PHDQLQJ
 $EVRUSWLRQRIZDWHU ±
 2[\JHQSHUPHDELOLW\PVHF 
 :DWHUSHUPHDELOLW\P˜P˜K 
 1D&OSHUPHDELOLW\PROH˜P˜K 
 7RXJKQHVVDWDVWUHWFKLQJ 3  
 5HODWLYHWHQVLOHHORQJDWLRQ 
 3HUPHDELOLW\RIOLJKW 
As a result of increased oxygen permeability and
high refraction index nD of lenses stand out for comfort
at operation that allows wearing them on an eye for a long
time without fatigability.
The carried out researches of synthesis and structure
formation laws of PVP copolymers have also allowed to
develop a material with increased elasticity properties in a
hydrated condition, that enables to make from it ultra-thin
contact lenses of new generation retaining high operational
properties even at thickness of 0.04 mm [4].
Good permeability for series of substances,
including medicinal solutions, compatibility with tissues
and acceptability has caused use of the synthesized
copolymers for medical ophthalmologic elements of the
various forms
The comparative clinical tests about the state of
eye-sight without correction are carried out. From 163
patients having an eye-sight without correction less 0.1,
after correction by means of contact lenses an acuteness
of eye-sight has increased for more than in 80 % and was
equal to 0.85–1.0. The research of an epithelial integument
of a cornea condition carried out in a various terms after
acclimatization at all the patients has shown, that
infringement of integrity crates membranes of an
epithelium of a cornea does not occur. And only at 6
patients after long continuous application of lenses (more
than 3 days) was observed a mild epithelium reddening.
3. Conclusion
Thus, copolymers developed on the basis of
compositions of methacrylic esters with polyvinyl-
pyrrolidone turned out to be suitable for the obtaining of
medical and correcting contact lenses of a new generation
with high operating properties.
References
[1] Crassous G. and Jozephovich M.: Biomaterials, 1984, 5 (3),
153.
[2] Suberlyak O., Skorokhoda V. and Levitsky V.: Ukr.Polym.J.,
1995, 5,177.
[3] Suberljak O., Skorokhoda V., Benedyk N. and Jaremkevych
S. Sposib oderzhannja gidrofil’nyh polimeriv. Patent Ukrainy
N37936À 15.05.2001.
[4] Suberljak O., Skorokhoda V. and Levytskyj V.: Khim. prom.
Ukrajiny, 2002, 4, 19.
ÎÑÎÁËÈÂÎÑÒ² ÑÈÍÒÅÇÓ ÊÎÏÎ˲ÌÅвÂ
ÏÎ˲²ͲËϲÐÎ˲ÄÎÍÓ ÄËß ÊÎÍÒÀÊÒÍÈÕ Ë²ÍÇ
Àíîòàö³ÿ. Ïðèâåäåí³ ðåçóëüòàòè äîñë³äæåíü
çàêîíîì³ðíîñòåé ñèíòåçó ã³äðîãåë³â íà îñíîâ³ êîïîë³ìåð³â 2-
ã³äðîêñ³åòèëìåòàêðèëàòó ç ïîë³â³í³ëï³ðîë³äîíîì òà åôåêòèâí³
øëÿõè ðåãóëþâàííÿ ¿õ âëàñòèâîñòåé. Ñèíòåçîâàí³ êîïîë³ìåðè
âèÿâèëèñü åôåêòèâíèìè ìàòåð³àëàìè äëÿ âèðîáíèöòâà
ã³äðîô³ëüíèõ êîíòàêòíèõ ë³íç.
Êëþ÷îâ³ ñëîâà: ã³äðîãåëü, ïîë³â³í³ëï³ðîë³äîí,
2-ã³äðîêñ³åòèëìåòàêðèëàò, êîíòàêòí³ ë³íçè.
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 1, No. 2, 2007 Chemical technology

Yevgen Kovalov

PRODUCTION AND QUALITY OF BLAST FURNACE COKE IN UKRAINE

Ukrainian State Research Institute for Carbochemistry UKHIN
7 Vesnina Str., Kharkov 61023, Ukraine
nto@ukhin.org.ua
Received: May 16, 2007

Abstract. This research displays the state of metallurgical
coke production in Ukrainew with special attention to the
raw material base for production of coke and its quality.
Besides the following essay deals with the detailed analysis
of preparation methods of coal charge for coking,
including thermal treatment and stamp charging and
formulates the main ways of upgrading coke quality
considering the rational technology of coking.
Key words: coal, coal blends, coke, blast furnace coke,
coke production, preheated blends, stamped blends, coke
structure, blast-furnaces melting, coke reactivity
in Ukraine will increase the production of iron to 35.5 m
tonnes (by 7.3 %) [1].
Powerful iron and steel industry of Ukraine requires
a lot of coke. Our country takes the fourth place in the
world production of coke after China, Japan and Russia.
For the past five years the output of coke in Ukraine,
after its maximum at 22m tpy in 2004, decreased to a
level of 19.2m tpy in 2006, but the contribution of the
coke producers in 2006 was somewhat different
compared to 2005 (Fig. 2).


 
Ukraine has 56 operational coke oven batteries the 

total capacity of which is about 24m tonnes per year of 

bulk coke of 6 % moisture. 




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<HDU
Fig. 1. Production of coke in Ukraine
The output of coke in Ukraine is determined in the
first place by its consumption first of all by metallurgical
plants to produce cast iron. It should be noted that after a
sharp decline in production of metal products during the
last years of the former Soviet Union the production of
iron steadily grows in the independent Ukraine during 16
years. In 2006 the maximal level was reached for all these
years – 32.7m tonnes. According to the Ukrainian
Association Metallurgprom, in 2007 the metallurgical plants
The reasons of such a decline, in our opinion, are
as follows:
· improvement of blast furnace operation, resulting

in gradual reduction of the specific coke rate (last decade
this index decreased from 630 kg to 508.5 kg per tonne
of hot metal);
· more stringent requirements to the quality of coke
that predetermines the coke rate,
· excess of imports of coke (mainly from Russia
and Poland) over its exports.
All these reasons are interconnected. They are
based mainly on discrepancy in the required and real
quality of coke due to the features of the available coal
base at Ukrainian coke works.
Table 1 presents the properties of blends from
typical Ukrainian coals compared to similar properties for
the leading world coke producers.
92 Yevgen Kovalov

Table 1 We should also note an unfavorable composition

Properties of coal blends and main process of the mineral part of typical Ukrainian coals and cokes
parameters of cokemaking produced from them. The basicity index of the mineral
1XPHULFDOYDOXHV part of the most coals in the Donbass (the ratio of total
,QGLFHVDQGXQLWVRIPHDVXUH
8NUDLQH /HDGLQJ content of basic sodium, potassium, calcium,
W\SLFDO ZRUOG magnesium and iron oxides in the ash of coals to total
FRDOV SURGXFHUV acidic oxides of silicon and amphoteric aluminum) is in
&RDOEOHQG the range 0.25-0.35. At the same time, to obtain coke
$VK$GGU\EDVLV  d with the strength after reaction CSR e”60 % the basicity
7RWDOVXOSKXU6GWGU\EDVLV d d index must not exceed 0.16, and for CSR e”65 % it
9RODWLOHPDWWHU9GDIGU\DVK  d should be no more than 0.12 provided all the other
IUHHEDVLV properties (reflectance, ash, sulphur, volatile matter,
3ODVWLFOD\HU\PP   etc.) also conform to the requirements to coals shown
%DVLFLW\RIDVK  d in Table 1 [3].
0HDQDUELWUDU\YLWULQLWHUHIOHFWDQFH d t In addition, our attention is drawn by rather high
LQGH[5R carbonizing rates at the coke works in Ukraine. The bulk
1RQXQLIRUPLW\LQGH[RIEOHQGE\   of coke oven batteries in Ukraine has the width of coking
YLWULQLWHUDQN 5   chambers 410 mm, the design carbonizing time 15 hrs
&DUERQL]DWLRQSDUDPHWHUV that corresponds to a carbonizing rate of 27.3 mm/hr.
WHPSHUDWXUH  t t Usually coke is obtained, as a rule, at significantly less
&DUERQL]LQJUDWHPPKU d d rates, for example, at the Australian company BHP Steel
the carbonizing rate does not exceed 24 mm/hr. This
rate would be equivalent to the carbonizing time 17 hrs
The distinctive feature of typical Donbass coals in coking chambers of the Giprokoks design of 410 mm
(main source of coking coals for Ukraine coke works) is wide [4].
their genetically high level of sulphur in the first line due At present there is a clear tendency in the coke
to pyritic sulphur [2]. industry of Ukraine to use some of the technologies
Low rank coals with high volatile matter and low developed earlier for production of coke from poorly
vitrinite reflectance prevail in the geological reserves and caking coals to obtain coke meeting modern
coals mined in Ukraine. The share of domestic high rank requirements by the NSC test and good for blast
coking coals (mean reflectance index of vitrinite above furnaces with PCI. First of all, these are the technologies
1.0 %) in the raw material base of the coke works in of coking of the preheated blend and coking of the
Ukraine is very insignificant. As a result, in spite of stamped blend.
introduction of high rank coals from other coal basins Preheated blend is carbonized in ovens with a useful
(first of all from Kuznetsk in Russia), the yield of volatile volume of 21.6 m3, 4.3 m high and 410 mm wide. The
use of preheated blend allows the coke battery output to
matter from coal blends at the coke works in Ukraine (on
be increased by 40 %.
the dry ash free basis) is 29-32 %, and the mean index of
There is a pilot plant at the JSC Yasinovsky Coke
vitrinite reflectance does not exceed 1.0 %.
Works for thermal treatment of coal blends of a design
According to the Metallurgprom, Ukraine produces
capacity of 60 t/hr of wet coal. The blend is dried and
around 18m tonnes of coking coals per year, however
preheated to 200 îÑ in two stages by means of rapid heating
coke works need at least 29.5m tonnes to meet the demand with a gaseous heat carrier in a stream.
of blast furnace operators. In addition, for the coke Thermal treatment of coal allowed significant
production high grade coals are required but some of reduction in the cost of coal blend used for coking due to
them are not available in Ukraine. The missing amount is the use of up to 70 % of low rank gas coals. The coke
made up with imports, mainly from Russia, in the amount produced is mainly sent to blast furnaces operated without
of about 11m tpy. However, in Russia due to the growth PCI. At present researches are carried out into the
of metal production, coking coals become more and more production of coke of improved quality from preheated
scarce, therefore the supplies to Ukraine do not always blend for application in blast furnaces with pulverized coal
meet the characteristics required for the production of injection.
high quality coke. Stamp charging has been successfully used during
Very promising are the imports of high quality coals a long time (since 1993) on coke oven battery No. 9-bis
from abroad (Australia, the USA, Canada). However, for at the Alchevskkoks [5-6]. In August 2006 battery No.
the reception of cargo vessels with coal specifically 10-bis was put into operation where stamp charging was
equipped terminals should be available in Ukrainian ports. introduced.
 Production and Quality of Blast Furnace Coke in Ukraine 93

 3 R R U O\  F D N LQ J 
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: H OOF D N LQ J 
F R D OV  E H OR Z    

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0 ±
0 ±
0 ±

Fig. 3. Coke from preheated blend

Initially the stamping technology as well as Table 2

preheating was considered mainly as the ways of retaining Quality of coke at Ukrainian coke works
coke quality due to the cost reduction of blends by using
a higher percentage of cheap coals with a lower caking %ODVWIXUQDFH
capacity. The blends used for stamping contained a lower ,QGLFHVDQGXQLWVRIPHDVXUH :LWKRXW
:LWK3&,
amount of fat coals and practically no coking coals. At 3&,
the time being more actual is a task of improving coke 5HDFWLYLW\&5,  d
quality. This task is solved by the use of blends with higher 6WUHQJWKDIWHUUHDFWLRQ&65  t
caking capacity and higher vitrinite reflectance index. 0HFKDQLFDOVWUHQJWKE\PLFXPWHVW  
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   It should be noted that recently the sulphur content


in Ukrainian cokes has decreased significantly

* 

   (by 0.5-1.0 %) due to the increasing imports of coking

*=K2   coals with lower sulphur from other countries. This has
=K 

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  brought some improvement in the reactivity and strength
6 6
 &RQYHQWLRQDOSURFHVV after reaction of coke. But it is not possible to ensure that

%OHQG FRPSRVLWLRQ
7  6WDPSFKDUJLQJ the level of these indices will meet the requirements of the
leading world producers of iron, because due to the
Fig. 4. Coke from stamp blend shortage of coking coals in our main suppliers (first of all
in Russia) the coal imported to Ukraine is characterized
Table 2 shows the generalized data on the quality by insufficient reflectance index of vitrinite and frequently
of coke obtained at Ukrainian coke works and used for by unfavorable chemical composition of ash.
blast furnace operation with and without pulverized coal On the whole, the quality of coke for blast furnaces
injection (PCI) [7]. without PCI corresponds to the requirements showing a
As is evident from Table 2, coke for blast furnaces rather low specific coke rate for producing hot metal –
without PCI is characterized by inferior reactivity and 508.5 kg/t. Technological possibilities of improvement of
strength after reaction indices determined by the Nippon coke rate in the blast furnace without PCI are nearing
Steel method. This coke is also inferior to that of the leading their exhaustion. This index was reducing during 1995-
world producers in mechanical strength by the micum test.. 2004 on average over Ukraine by 10-15 kg/t annually;
Also a higher ash and sulphur of coke calls our attention. since 2005 it was stabilized.
94 Yevgen Kovalov

In order to keep the competitiveness of the Ukrainian Ukrainian steel producers: Mittal Steel Krivoy Rog,
metal products on the world market it is necessary to develop Alchevsk Iron and Steel Plant, Azovstal Iron and Steel
iron making technologies by using pulverized coal injection. Plant, Zaporozhstal Iron and Steel Plant. As is well known
For the time being there is a single unit of such a type in PCI requires coke of higher quality. Therefore we should
Ukraine at blast furnace No. 2, JSC Donetsk Metallurgical expect in the nearest years a sharp increase in the
Plant. Hot metal is produced without using natural gas, the requirements of the Ukrainian blast-furnace operators to
consumption of pulverized fuel has been lately 160-170 kg/t the quality of coke.
of hot metal, that allowed the reduction of coke rate to The results of two series of blast furnace tests using
390 kg/t. The coke used in that blast furnace actually coke of improved quality under the supervision of
completely satisfies the requirements of world standards as specialists of UKHIN are presented in Table 3. The first
is evident from Table 2. This is ensured by using in coal series was run on blast furnace No. 5 with a useful volume
blends high quality coal from some of the Ukrainian coal of 1513 m3 [8] at the Azovstal Iron and Steel Plant. The
mines (for example, the Krasnoarmeiskaya Zapadnaya Mine). blast furnace does not use PCI, though, as mentioned
Now intensive work is being undertaken to introduce before, work is being conducted in this direction.
PCI technology in blast furnaces by a number of major

Table 3
Quality of coke for blast furnace tests

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As is evident from Table 3, coke for blast furnace rose by 10.5 %, the specific coke rate decreased by 32
No. 5 had much better quality than that used traditionally kg/t hot metal.
in blast furnaces without PCI. These results enabled another series of blast furnace
The quality of blend used to produce coke for blast tests on blast furnace No. 2 with a useful volume of 1033 m3
furnace operation during the base and test periods is shown at the JSC Donetsk Metallurgical Plant where PCI is used at
in Fig. 5. the rate 160-170 kg/t hot metal. The use of a high quality coke
The use of such coke allowed a significant increased the productivity of the blast furnace by 17.1 % and
improvement of the blast furnace operation: its productivity reduced the coke rate by 51 kg/t hot metal (Table 4) [7].

 
$]RYVWDO,URQDQG6WHHO 'RQHWVN
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Fig. 5. Coke blend for blast furnace tests

 Production and Quality of Blast Furnace Coke in Ukraine 95

Table 4
Results of blast furnace tests
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In addition, this coke allowed a number of process 

2EMHFW &5, &65
parameters to be improved (to raise the air-blast
temperature, to eliminate unscheduled down time and slow
run of furnace). 3LWFK FRNH    
The tests done showed the possibility of production
of coke from Ukrainian coals in accordance with the
requirements of the leading world steel producers. Here
the positive effect of upgrading coke quality is significantly 3HWUROHXP    
FRNH
higher when using PCI.
That is why UKHIN jointly with the coke works of
Ukraine undertakes the work aimed at the improvement 3\URFDUERQ     
of quality of coke. Here we believe that the basis of coke
properties lies in its structural characteristics and the main
attention should be paid to the production of coke with Fig. 7. Reactivity and strength of some carbonaceous
the required structure. materials
It is well known that carbon of coke represents a
composition of ordered (anisotropic) and disordered Reactions of carbon oxidation proceed with a lower
(isotropic) carbon. Therefore reactivity of coke is a gross rate in coke with anisotropic structure that allows the coke
index and it reflects the chemical activity of all the charge in the blast furnace to retain the required strength
components of the carbon composition when reacting with and permeability when descending to the low levels of the
carbon dioxide. blast furnace.
The reactivity of different types of coke texture is In our opinion, blast furnace coke with a
different. The higher total anisotropic carbon in coke and predetermined content of anisotropic structures can be
the larger size of anisotropic structures the lower is its produced by using coal blends with the required properties
reactivity. Fig. 6 illustrates this situation [9]. (including the introduction of organic mesogenic additives)
and rational technological parameters of carbonization.
 
*ORZUDQN
WRFDUERQGLR[LGH
Conclusions

 1. Coke production in the future is related not only
WRR[LJHQ to the amount of iron produced but also to the improvement
5HDFWLYLW\PJJÂPLQ


of coke quality. The high coke quality will allow both the
 reduction of coke imports to Ukraine and an increase of
=KPHGLXPUDQN
 the export potential of the coke industry, i.e. this will favor
6KLJKUDQN
 the growth of coke production. At the same time, the

FRNLQJ improvement in quality of coke will result in a decrease of
the coke rate for smelting iron and will decrease a demand

for it of metallurgical plants in our country.
 2. Coke facilities available in Ukraine are quite
$   $   $   $  
enough to completely satisfy the needs of Ukraine in met
Fig. 6. Dependence of coke reactivity on contents coke. However, resources and output of coking coals in
of anisotropic carbon Ukraine are not sufficient to provide enough raw stock
for coke producing facilities. Therefore, in addition to
The results of our tests on model carbon materials increased mining of domestic coals it is necessary to import
showed that the more ordered the carbon structure the coking coals, to introduce the technologies aimed at
lower is its reactivity determined by the Nippon Steel widening the raw material base for coking and improving
method (Fig. 7). the quality of met coke.
96 Yevgen Kovalov
3. The main trends of improving the quality of coke
which are developed by Ukrainian scientists and blast
furnace and coke oven operators are the following:
3.1. Development of a rational raw material base
for coking:
- formation of the required of quality of coal blends
for the ash content, sulphur, rank by better washing and
reduction of ash in coal concentrates;
- raising of uniformity of coal in terms of its
petrographic composition;
- reduction of the sulphur content and raising of
coal rank by increasing the output of Ukrainian low sulphur
coal and imports of high rank coals;
- addition of organic mesogenic substances and
anisotropic materials to the blend.
4. Rational cokemaking technology, that is
control of physical and chemical coking processes to
transform the isotropic texture of coke to anisotropic
one (higher degree of ordering of coke carbon) by
reduction of carbonizing rates to the level of no more
than 24 mm/hr, by rational level of final temperatures
of carbonization and by additional soaking of coke in
coking chambers.
5. Postcarbonization treatment of coke: dry
quenching with soaking of coke in the forechamber and
additional mechanical treatment of coke to realize
mechanical stresses and fissuring.
6. For Ukraine which is lacking in considerable
domestic sources of oil and natural gas and dependent on
the imports of these power resources the use of chemical
and power potential of coking coals is very actual.
Therefore there are a lot of chemical divisions at our coke
works for processing carbonization by-products. Their
final products contribute 40-50 % to the total profit of the
coke works. By using coke dry quenching units and by
burning excess coke oven gas in heat-and-power plants
our coke works can further increase electric power
generation.
References
[1] Rudyka V.I.: Uglekhimichesky Zhurnal, 2006, 5-6, 3.
[2] Miroshnichenko D.V., Bliznyuk T.N. and Toryanik E.V.:
Uglekhimichesky Zhurnal, 2003, 5-6, 47.
[3] Leonard D.C., Bonte L., Dufor A. et al.: Coke quality
requirements of European blast furnace engeneers. 3 rd
International Cokemaking Congress. 1996, 1.
[4] Kovalov E.T., Shmalko V.M., Shulga I.V. and Ryschenko
A.I.: Uglekhimichesky Zhurnal, 2006, 5-6, 13.
[5] Karpov A.V., Kuznichenko V.M. and Lobov A.A.: Koks i
Khimia, 1997, 8, 9.
[6] Chub V.E., Krivonos V.V., Dzikunov S.N. et al.: Koks i
Khimia, 2003, 12, 14.
[7] Ryzhenkov A.N., Gordienko A.I., Kovalov E.T. and Shulga
I.V.: Requirements to the quality of coke for blast furnace
using pulverized fuel and industrial experience of production
of this coke. Trudy mezhdunarodnoy nauchno-tekhnicheskoy
konferentsii “Pyleugolnoye toplivo – alternativa pryrodnomu
gazu pri vyplavke chuguna”. 18-21 December 2006, Donetsk,
Ukraine.
[8] Buga I.D., Bondarchuk P.I., Ryschenko F.I. et al.:
Uglekhimichesky Zhurnal, 2006, 3-4, 47.
[9] Sklyar M.G., Slobodskoy S.A. and Dang V.H.: Koks i
Khimia, 1988, 3, 9.
ÂÈÐÎÁÍÈÖÒÂÎ ² ßʲÑÒÜ
ÄÎÌÅÍÍÎÃÎ ÊÎÊÑÓ Â ÓÊÐÀ¯Í²
Àíîòàö³ÿ. Íàäàíî ñòàí âèðîáíèöòâà ìåòàëóðã³éíîãî
êîêñó â Óêðà¿í³. Îñîáëèâà óâàãà çâåðíåíà íà ñèðîâèííó áàçó
âèðîáíèöòâà êîêñó òà éîãî ÿê³ñòü. Çðîáëåíî äåòàëüíèé àíàë³ç
ñïîñîá³â ï³äãîòîâêè âóã³ëüíî¿ øèõòè äëÿ êîêñóâàííÿ,
âêëþ÷àþ÷è òåðì³÷íó ï³äãîòîâêó òà òðàìáóâàííÿ øèõòè.
Ñôîðìóëüîâàíî îñíîâí³ øëÿõè ï³äâèùåííÿ ÿêîñò³ êîêñó.
Ðîçãëÿíóòî ðàö³îíàëüíó òåõíîëîã³þ êîêñóâàííÿ..
Êëþ÷îâ³ ñëîâà: âóã³ëëÿ, øèõòà, äîìåííèé êîêñ,
âèðîáíèöòâî êîêñó, òåðì³÷íà ï³äãîòîâêà, òðàìáóâàííÿ øèõòè,
ñòðóêòóðà êîêñó, äîìåíí³ ïëàâêè, ðåàêö³éíà çäàòí³ñòü, ñóõå
ãàñ³ííÿ êîêñó
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 1, No. 2, 2007
Leonid Zhelezny, Yevgen Kobylyansky and Oleg Mishchuk
INFLUENCE OF THE NATURE OF A DISPERSED PHASE ON
ANTIWEAR PROPERTIES OF HIGH TEMPERATURE GREASES
Ukrainian Scientific and Research Institute for Oil Refining Industry “MASMA”
46, Palladin avn., Kyiv – 142, 03680, Ukraine
masma@svitonline.com
Received: May 16, 2007
Abstract. Antiwear properties of modern high temperature
greases have been studied by simulating various temperature
and load conditions on friction machines. Differences in
tribological characteristics of greases depending on the
nature of their thickeners were determined and explained.
Maximum antiwear properties were revealed in conventional
complex and overbased complex calcium salicylate,
sulfonate and phenolate greases.
Key words: high temperature greases, dispersed phase,
dispersion medium, antiwear properties, wear scar
diameter.
1. Introduction
The main function of antifriction greases is the
prolongation of the service life of machines and
mechanisms at the cost of friction and wear reduction of
their moving parts and the elimination of seizure and
jamming processes of conjugated friction surfaces.
Despite a great number of works devoted to the research
of tribological properties of lubricating materials, the
generalizations pertaining to the influence of a dispersion
medium and thickener upon lubricating ability of various
types of greases are not quite sufficient and those given
in the available literature sources are very often
contradictory [1,2]. Intensive scientific studies in this field
were performed in 60-80-ties of the past century. Lithium,
sodium, hydrated and complex calcium greases as well
as some greases based on organic and inorganic thickeners
were the main objects of research in those years.
Tribological properties of greases were researched mostly
with the purpose of selecting the optimal composition of
additives. The lubricating ability of basic greases was not
practically studied in spite of the fact that many general
purpose greases even without antiwear and extreme
pressure additives in their composition are capable of
providing the normal work of friction units within certain
ranges of speeds and loads.
Chemical technology
The possibility of formation of boundary lubricating
films and their influence on mechanical and chemical
conversions of a friction surface were proved by numerous
scientific works which were the basis of modern ideas of
friction, wear and lubrication [3, 4]. It was found out that
a lubricating ability is a complex function of composition,
structure and physico-chemical properties of greases and
friction surfaces. Structurized spatial structure of greases
with specific bulk and mechanical properties as well as
the presence of different surface active substances in
their composition has given the grounds to consider that
lubrication action is connected with bulk and adsorptive,
in particular, hemisorption actions.
In recent years the assortment of antifriction
greases has been considerably extended and now the
market of lubricating greases is represented with a number
of high temperature products with diverse spectrum of
thickeners used. Due to broadening of a temperature range,
the increase of speeds and loads in operating equipment,
the enhancement of its power and capacity and,
consequently, with growing hard requirements for
lubricating materials, it is exactly high temperature greases
( with dropping point not less than 503 K) are playing the
leading roles both in production volumes and in application.
Proper selection of such greases, their effective and rational
use allows to substantially lower the energy consumption
bringing about a significant economy of power.
2. Experimental
In the proposed work, it the lubricating ability of
the most widespread high temperature greases has been
investigated with the purpose of determining the
connection between the nature of a dispersed phase and
tribological characteristics of a dispersion medium
(petroleum oil) thickened by it as well as to find out the
most effective thickeners. Complex soap greases which
have been thickened by anionically complex soaps
representing by themselves either adsorptive or molecular
98 Leonid Zhelezny et al.
complex of soap of higher fatty acid and salts of low
molecular organic or mineral acids and also greases based
on highly dispersed modified silicon oxide (pyrogenic silica
gel or aerosile), organo-substituted mineral (bentonite),
urea derivatives, complex overbased calcium sulfonates,
salicylates and phenolates have been tested.
All samples of greases were prepared in accordance
with the energy saving technologies making it possible to
optimize the temperature regime of greases preparation,
to reduce the number of stages of a technological process
and to significantly decrease a production cycle. Petroleum
oil containing 72.0 % of mass paraffino-naphthenic
hydrocarbons, 21.6 % of light and 4.7 % of middle
aromatics as well as 1.7 % of resins have been used as
the dispersion medium for greases. The penetration index
of model grease samples was equal to 265±5 m”10-4
(GOST 5346), the dropping point – 503-543 K (GOST
7693, for greases on aerosile and bentonite such index is
not available), the content of free alkalis in complex soap
greases in conversion to NaOH – 0.1-0.2 % (GOST 6707),
the base number of overbased greases ~250 mg KOH/g.
The ability of petroleum oil and greases to reduce
wear over the range of loads 392- 748 N on its basis have
been evaluated in four ball friction machine at 293 K
according to GOST 9490. Wear scar diameters (Di ) of
modal systems at higher (elevated) temperatures have been
determined after ASTM D 226 in Falex four ball friction
machine (load – 392 N, frequency of rotations – 1200
min -1). At this point it is necessary to consider the
following. It is well-known [5] that the structure of SHkH-
Antiwear properties of high temperature greases
15 steel of which the balls of a friction pair are made, is
changed within the range of temperatures from 353 to
523 K. This results in inhomogeneous micro scratching
produced with wear particles during friction at elevated
temperatures on the surfaces of steel balls (scoring). Micro
scratches can appear in a compression zone far away
beyond the friction zone limits and should not be
considered during evaluation of a wear scar diameter.
Otherwise this can be the reason of significant errors in
experimental data.
3. Results and Discussion
Antiwear action of greases in four ball friction
machine is provided mainly due to the formation of a
boundary lubricating film on a metal surface (~ 1 mkm)
with a large number of molecular layers, the anisotropy
of mechanical properties, high resistance to great normal
loads and low – to the action of circumferential stresses
as is also due to the chemical conversions on a friction
surface [4]. Wear of a friction surface at 196 N and
293 K, as it is proved by the data presented in the Table, is
negligible and a friction process depends to a small degree
upon the nature, polarity and chemical activity of the
components of a grease thickener. Higher antiwear
properties of base oil can be explained by a high rate of
oxygen diffusion to a friction surface because of the lower
viscosity of oil in comparison with greases and the
subsequent formation of active oxygen-containing
compounds preventing the wear.
Table
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 Influence of the Nature of a Dispersed Phase...
A physico-chemical activity of greases in the
process of friction, that is, kinetics of the interaction of
active grease components with metal surface and the
relationship between the rate of a strong boundary film
formation or mechano-chemically modified surface layer
and their destruction gained in importance when increasing
loads in our experiments from 196 up to 748 N. At the
maximum load (784 N), as it is evident from the data
presented in the Table given below, the antiwear action of
all greases is much superior to the analogical index of
their dispersion medium – petroleum oil. Since the
composition of greases contains surface active substances
– elements of a thickener and technological surfactants
(TSA), precisely their polarity, dimensions and structure
of molecules determine the adsorptive activity and, in the
end, the strength of boundary layer and the ability to deform
a surface layer of metal.
At the load of 392 N, most thickeners improve
antiwear properties of a dispersion medium. Polyurea or
urea (Ur-) grease and lithium complex grease are
characterized by the minimum “Di” which is equal to 0.50
mm. For some modal samples, however, thickening of oil
with certain complex thickeners does not influence on
the lubricating ability of the initial dispersion medium, since
the structure of greases is destroyed at normal shearing
stresses in a friction zone. Complex aluminum (cAL-)
aswell as inorganic thickeners such as bentonite (Bn-)
and especially aerosile (Si-) enhance “Di” of petroleum
oil. It should be pointed out that aluminum complex greases
are produced on practically nonpolar di-substituted
aluminum soap of stearic and benzoic acids which soap
forms complex branching polymer like structure due to
the coordination bonds between aluminum atoms of one
molecule and oxygen atoms of a hydroxyl group of the
other molecule of soap. As it is shown in [6], lowering of
the polarity of soap molecules reduces the lubricating ability
of greases based on petroleum dispersion media.
Si-grease, one of the objects of our research, has
been produced on aerosile modified with
dimethyldichlorinesiloxane (DMDCS). As a result of
modification, active centers of an aerosile surface are
excluded from interaction, the forces acting between
particles of the thickener as well as between the thickener
and the dispersion medium of grease are weakened [1].
Besides, in the process of friction at high contact loads, the
destruction of a boundary and modified layers, probably,
goes faster due to the weakness and instability of interaction
forces between the particles of aerosile and a steel surface.
The same regularities are evidently habitual to Bn-grease
being under friction and above-mentioned loads.
It was prepared on bentonite and modified with
dimethyldioctadecylammonium -chloride which is known
under the trade mark “Bentone-34”. The thickener has a
strongly developed micro porous structure with adsorbed
99
molecules of a modifier on the surface. However, on
increasing the severity of friction regimes, the surface
activity of surfactants (SAS) desorbed from particles of
a mineral and TSAS present in the grease turns out to be
insufficient to form a strong and stable boundary layer of
grease on a metal surface.
A sharp increase in “Di” is observed for Ur-grease
as loads growing higher. In order to understand the reasons
of this phenomenon it is necessary to consider the
structure of polyurea thickener. Depending on amines
(aliphatic, cyclic or aromatic) used for its preparation,
their ratio as well as temperature conditions during grease
production, a dispersed phase in a petroleum oil can acquire
a great variety of structural forms and the grease by itself
will significantly differ just in mechanical, colloid and
thermal stabilities as well as in high temperature properties
and lubricating ability. It is pointed out in the work [7]
that the presence of aryl amines in the composition of
polyurea thickener substantially enhances performance
characteristics of the grease and makes a positive effect
on the thickness and load carrying capacity of a lubricating
layer. For research studies, we have prepared a modal
sample of Ur-grease with balanced properties but that
required lowering the content of aromatic amine in the
thickener’s composition. The strength of a boundary
lubricating film on a steel surface at friction was decreased
that resulted in the significant rise of “Di” value at the load
of 784 N.
The strongest films on a steel surface are formed
under the influence of calcium complex greases (both
conventional cCa – and all three overbased calcium:
sulfonate (Su -), alkylsalicylate (As -) and phenolate (Fn -).
Their “Di” at maximum load 784 N are three times less
than in a petroleum oil. It is likely that calcium hydroxide
plays an important role in forming a boundary layer. In
cCa-grease, calcium hydroxide is present in a free form
and is also connected coordinationally with the structural
skeleton of cCa-grease which is formed by a complicated
calcium complex consisting of stearic and acetic acids.
Ca(OH)2 if compared with other alkalies, is less active,
moreover, higher degree of alkalies bonding by cCa-grease
due to the enhanced ability to form adsorptive complexes
[1] leads to minimum chemical conversions of friction
surface and the preservation of its initial strength. Authors
[8,9] explain the formation of complex calcium grease of
highly strong boundary layer that prevents wear of friction
surfaces at high loads as a result of calcite polymorphic
modification in carbonate nuclei of micellae – the main
cell of the structural skeleton of these greases. Nano-sized
petals of calcite of overbased sulfonate due to the
significant value of ratio of a surface area to volume have
an enormous surface activity owing to which they are
oriented in a lubricating film with the definite manner
forming a peculiar covering like fish scales and take an
100 Leonid Zhelezny et al.
active part in tribo-chemical conversions of surface
layers.A particular role is played by the constituents of
the overbased component of sulfonate complex grease,
namely, calcium metaborate being a part of micelle’s
nucleus and calcium 12-hydroxy stearate forming together
with calcium sulfonate the adsorptive envelope of grease.
Molecules of calcium metaborate loosens nuclei of
micellae, thus, intensifying the surface activity of calcite
due to increased defects of its particles’ surfaces and, in
this manner, facilitating the access of molecules of
sulfonate and calcium 12-hydroxy stearate to a metal
surface. A similar mechanism of a lubricating action is
probably typical of complex As- and Fn- greases [10].
On rising the temperature in a friction zone from
293 up to 423 K, the role of surfactants desorption process
from a surface friction as well as the chemical constituent
in the interaction process of the active components of
grease and a metal surface is growing in importance.
Moreover, the influence of oxygen on the processes of
boundary friction is enhanced. In this case it is suggested
[6] that oxygen presence and high temperatures are
beneficial to the intensive oxidation of a friction surface
and, consequently, to raising the adsorption of polar
ingredients contained in grease. At the same time, the
oxidation of a dispersion medium takes place, primarily,
naphthenes and light aromatics as well as other components
of grease and that results in rising of their surface activity.
It is suggested that chemically active components of
petroleum oil formed at high temperatures can interact
with a metal surface and make a sufficiently strong film
in order to withstand the load of 392 N and to prevent a
wear. Therefore, “Di” of a dispersion medium within the
range from 293 to 423 K is grown approximately by
0.15 mm only (see Table).
On increasing the depth of the oxidation of greases,
the deterioration of their antiwear properties becomes
appreciably evident. It is pointed out in a number of works
[1, 6] that there is a correlation between thermal oxidation
stability of some soap greases and their lubricating ability.
The data of the Table indicate that elevated
temperatures have particularly adverse effect on the
lubricating ability of Barium complex grease (cBr-). Within
the temperature range of 293-373 K, surfactants
desorption and chemical interaction of the components
of grease with steel do not promote a substantial rise of
“Di” index.
At 423K, however, the lubricating action of a
boundary layer is changed with a seizure due to the
intensification of oxidation processes, the destruction of
a lubricating film and the sharp activation of chemical
transformations. This causes the growth of “Di” index to
the maximum value (1.73 mm) amid all studied modal
greases at this temperature including their dispersion
medium (0.76 mm). It is conceivable that cBr-grease is
the most stable to oxidation because of the initiating action
of soaps and salts of acetic acid; this action manifests
itself after the complex thickener’s destruction. Similar
to cBr-grease, the growth of “Di” index for cAl-, cLi- and
Ur-greases with rising temperature is observed, but not
in such sharp form (see Table). This is likely to be
connected with the different thermal stability of films, the
different ability of greases to adhesion under these
conditions as well as their diverse stability to oxidation.
The rising of “Di” for 0.24 and 0.10 mm, respec-
tively, is characteristic of kNa- and Bn- greases at 373 K
in comparison with the same index at 293 and 423 K (see
Table). It is obvious that due to the differences in nature,
polarity and other characteristics of the thickeners of these
greases, the mechanism of their lubricating action causing
such anomalies is cardinally different. It can be suggested
that antiwear properties of kNa-grease at 373 K are
decreased because of the destruction of an adsorptive layer
on a metal, the weakening of bonds in kNa-thickener and
the intensification of oxidation, that is brought about,
among other things, by the induced action of sodium salts
of various acids uncombined in a complex and as for the
high temperature effect it is still insufficient for the
intensive chemical interaction of components of grease,
both present in it primordially and those newly formed,
with a metal surface producing new products which form
the strong boundary layer.
At temperature of 423 K, generated oxygen-containing
surfactants together with other substances having high
reactivity probably are capable of forming a stable lubricating
hemisorptive film which is by its strength in no way inferior
to that formed at 293 K but formed according to other
mechanism. Deterioration of Bn-grease antiwear properties
at 373 K is induced, possibly, by the desorption of bimolecular
layer of organic cations from the surface of bentonite, that is
molecularly combined modifier, the redistribution of the
molecules of surfactants on the surface of thickener and
metal, and, caused by these processes, the destruction of a
lubricating film. It can be also assumed that stabilization of a
system and “Di” reduction at 423 K is takeing place as the
consequence of adsorption of products of thermo chemical
and thermo oxidation changes of a dispersion medium on
the surfaces of bentonite’s particles and, especially, on the
surface of steel; all this results in the transformation of a
metal surface itself.
Conservation of antiwear properties on one and the
same level within a wide range of temperatures of Si-
grease on aerosile with a high degree of modification is
caused by thermostability of the grease as such and
conditioned by the nature of the adsorptive boundary layer
formed on a mineral. However, the possibility of DMDCS
molecules destruction with the following chlorine
penetration in a friction zone is not excluded under high
temperatures. This active element, under certain conditions,
can improve antiwear indices chemically polishing friction
surfaces, evenly distributing loads and, thus, reducing local
 Influence of the Nature of a Dispersed Phase...
temperatures and pressures [6]. It is quite possible that
the decrease, to some extent, of Si-grease’s “Di” index at
373 K is connected with the realization of the above
mentioned mechanism.
Antiwear properties of cCa-grease and overbased
calcium greases do not practically change within the
studied range of temperatures and remain very high ( “Di”
~ 0.55 mm). This affirms the efficiency of lubricating
and, probably, antioxidation action of the thickener’s
components of these greases, their capability to different
types of sorption and the interaction with metal surface
under high temperatures due to the availability of sufficient
quantity of active functional groups.
4. Conclusion
Thus, to protect steel surfaces under friction against
wear within a wide range of temperatures and loads under
conditions when other properties of general purpose
greases without antiwear and extreme pressure additives
are not so important, it is expedient to use conventional
complex (with periodical change of grease in a friction
unit) or overbased complex calcium salicylate, sulfonate
and phenolate greases (when grease is packed for the
whole service life of a friction unit).
References
[1] Ishchuk Yu.L.: Composition, Structure and Properties of
Lubricating Greases. Kyiv, 1996.
[2] Klamann D.K.: Greases and Related Products. Moskwa,
1984.
101
[3] Boden F.P. and Tabor D.: Friction and Lubrication of Solid
Bodies. Moskwa, 1968.
[4] Kostetsky B.I.: Surface Strength of Materials under
Friction. Kyiv, 1974.
[5] Blanter M.E.: Theory of Thermal Treatment. Moskwa, 1984.
[6] Fuks I.G. : Additives for Lubricating Greases. Moskwa,
1982.
[7] Mitsuoka M., Nakajima Y., Miyamoto Y. and Iwamatsu H.:
NLGI Spokesman, 2003, 5, 22.
[8] Hunt M.W.: Lubricating Engineering, 1975, 31, 183.
[9] Makedonsky O., Kobylyansky E. and Ishchuk Yu.:
Eurogrease, 2003, 5, 5.
[10] Papeykin O.O., Kobylyansky E.V., Zhelezny L.V.,
Kravchenko O.R. and Ishchuk Yu.L.: Lubes’n’Greases, 2006,
12, 44.
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ñó÷àñíèõ âèñîêîòåìïåðàòóðíèõ ìàñòèë ìîäåëþâàííÿì íà
ìàøèíàõ òåðòÿ ïðè ð³çíèõ òåìïåðàòóðàõ òà íàâàíòàæåííÿõ.
Âñòàíîâëåíà òà ïîÿñíåíà ð³çíèöÿ ó òðèáîëîã³÷íèõ
õàðàêòåðèñòèêàõ ìàñòèë â çàëåæíîñò³ â³ä ïðèðîäè ¿õ
çàãóñíèêà. Ìàêñèìàëüí³ ïðîòèçíîøóâàëüí³ âëàñòèâîñò³
âèÿâëåíî ó çâè÷àéíèõ êîìïëåêñíèõ ³ êîìïëåêñíèõ íàäëóæíèõ
ñàë³öèëàòíèõ, ñóëüôîíàòíèõ òà ôåíîëÿòíèõ êàëüö³ºâèõ
ìàñòèëàõ.
Êëþ÷îâ³ ñëîâà: âèñîêîòåìïåðàòóðí³ ìàñòèëà,
äèñïåðñíà ôàçà, äèñïåðñíå ñåðåäîâèùå, ïðîòèçíîøóâàëüí³
âëàñòèâîñò³, ä³àìåòð ïëÿìè çíîøóâàííÿ.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 1, No. 2, 2007
Yaroslav Vakhula, Victor Vasijchuk, Anna Romaniv and Oleg Semchuk
PECULIARITIES OF FORMATION
OF SOL-GEL COATINGS BASED ON WATER GLASS
Lviv Polytechnic National University
12 Bandera str., 79013 Lviv, Ukraine
sylikat@polynet.lviv.ua
Received: April 12, 2007
Abstract. The work deals with the development of
compositions of protective, insulating and decorative glass
coatings, as well as coating formation using sol-gel
technology. Conditions for the preparing of homogeneous
colloidal solutions necessary for the formation of coatings
and coating properties have been determined. The
peculiarities of glass coating formation based on water
glass have been developed.
Key words: sol-gel technology, glass coating, colloidal
solution, water glass.
1. Introduction
Modern science of materials faces the problem of
search and development of new materials with the complex
of high operational performances. Implementation of
modern requirement is possible at application of different
surface coatings. Glassy and glass-ceramic coatings are
of special interest among bulk of coating materials.
Glassy materials are widely used in different
branches of industry. They increase durability and quality
of various products made from metal, plastic mass, glass
and ceramics. Moreover, they impart the necessary technical
properties to the surface of metals. Depending on service
conditions, as well as nature, form and sizes of products
on which glassy coatings are applied, compositions of glass
and methods of coating formation may be chosen.
Majority of glass coatings is obtained in a silicate,
borate and silicophosphate systems. However, most
number of coatings of polyfunctional purpose are
developed in the silicate system which is successfully used
in many spheres. Silicate glass is characterized by high
durability, corrosion resistance and thermomechanical
properties. The choice of formation method depends not
only on properties and form of undercoat or necessary
parameters of coating but also on its chemical composition.
One of perspective methods of glass coating
formation is a sedimentaion method out of film-forming
solutions [1, 2]. This method is based on the use of true
solutions which contain water-soluble salts of ingredients.
The main requirement to solution is absence of coagulation
and ability of sediment formation.
Chemical technology
Glass coatings obtained from sol and colloidal
solutions have substantial advantages comparing with those
obtained via traditional trailing technology. Glass coatings
form compact gas-proof film over surface of undercoat.
Moreover, they have a row of important advantages over
traditional coatings: lower molding temperature, less
thickness and greater flexibility. The difference between
coefficient of linear expansion of coating and undercoat
during their application is less perceptible.
As it was mentioned above, silicate coatings form
a large group. Among the perspective methods of their
forming sol-gel method is of special interest. It’s caused
not only by high quality of coatings, but also by the
considerable energy-saving. It should be noted that
colloidal silicate solutions have special gelanizationing
susceptibility, which allows to obtain gels and accordingly
glass coatings in short time.
In practice most researchers use the products of
complete or partial hydrolysis and polycondensation of
tetraetoxysilane Si(OC2H5)4 and other alcosilanes for the
obtaining of colloidal silicate solutions [3, 4]. Silicium oxide
should be introduced into solution composition using aqueous
solution of alkaline silicates, so called water glass [5].
2. Results and Discussion
The detailed analysis of influence of individual
oxides on glass properties allowed to develope the system
of prognostication of choice of chemical composition of
colloidal solutions depending on silicium-containing
component for the formation of glassy and glass-ceramic
coatings for glass, ceramics and metals.
Forecast scheme for the choice of chemical
composition of industrial coatings based on water glass is
shown in Fig. 1.
Thus, the alkaline silicate systems (soluble glass)
have wide range of compositions, which are characterized
by different alkalinity and nature of cations. Apparently,
those solutions of lithium, sodium and potassium silicates
are of special interest for the obtaining of coating.
104 Yaroslav Vakhula et al.


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Fig. 1. Forecast scheme of chemical composition choice of glass coating based on water glass
The essence of coating formation technology
consists in spraying of colloidal solution over hot surface
of undercoat followed by heat treatment. For the obtaining
of glass-ceramic coatings undercoat surface was
additionally treated at the temperature of crystallization.
In the case of obtaining of decorative glass coating, the
suspension of gel powder was applied to undercoat surface
followed by heating.
2.1. SiO2-(Na2O+K2O)-R2O3 system
(on the basis of Na – water glass system)
Introduction of the limited amount of R2O3 oxides
(e.g. B2O3, Al2O3) into composition of glass considerably
increases corrosion resistance and mechanical durability.
The presence of B2O3 decreases viscosity and improves
forming property of glass bath.
Composition of protective coating based on water
glass was chosen by taking into account the previous
results of researches and specific of preparation of colloid
solutions stable to gelanization. Composition of protective
coating based on water glass is represented in Table 1.
Table 1
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Composition and coefficient of linear expansion
of glass coatings
Sodium water glass (M = 3.5), sodium aluminate,
boric acid and to potassium hydroxide were used for
introduction of the indicated oxides to composition of
glass coating and obtaining of solutions stable to
gelanization. 1-4 % of K2O in glass bath decreases its
viscosity, extends the interval of coating forming, and
increases corrosion resistance of glass.
2.2. SiO2-(Li2O+K2O)-BaO-R2O3
system (on the basis of Li, K –
water glass system)
Taking into account the influence of oxides on
glass properties and technological features of the offered
method, Li2O-K2O-BaO-B2O3-Al2O3-SiO 2 system was
chosen for the obtaining of glass-ceramics insulating
coatings. The peculiarity of such system is the availability
of two alkaline oxides, what increases electro-resistance
and decreases softening temperature. Moreover, BaO
provides the coatings with dielectric properties, as well
as improves crystallization ability of glass.
Composition of glass chosen for the synthesis of
glass-ceramic coatings is presented in Table 2.
One can see from Table 2 that in compositions
FDOFXODWLRQV
12-14 there is an increase of BaO content owing to B2O3.
       Li2O/K2O ratio is constant and equal to 1. Such ratio is
       necessary for the obtaining of glass with high dielectric
       properties. At constant basic of the components, the
       increase of SiO2 in compositions of glass 15-17 increases
      
       electrical resistance. The conducted calculations confirm
       the forecasts.
       Lithium and potassium water glasses, as well as
       lithium hydroxide, boric acid, barium and aluminium
      
      
nitrates were used for the preparation of solutions.
 Peculiarities of Formation of Sol-gel Coatings Based on Water Glass 105

Table 2
Composition of glass
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2.3. K2 O-Al2O3-B2O3-SiO2-P2O5 system collapses in the air. Modification of glass composition may
(on the basis of K – water glass system) increase its chemical stability.
Since the majority of phosphatic glasses have low
Decorative glass coatings are widely used in chemical stability and collapse under the action of air
finishing of wares from glass, ceramics and metal. Low moisture the synthesis of K 2O-SiO 2-P 2O 5 system is
forming temperature, high chemical stability and high- foreseen by adding of Al2O3 and B2O3, both separately,
quality colouring are the main requirements to meet. and jointly.
Compositions of glass with the variable amount of
6L2

P2O5 (48.0-54.0 mol %) is presented in Fig. 3. The Al2O3
content is 2.0-8.0 mol %, accordingly. The net of
compositions allows to cover all possible variants with
  the purpose to receive chemically stable glass with the
low temperature of his synthesis.


Potassium water glass, potassium aluminate,
ammonium, boric acid and to potassium hydroxide were

z 
z 
used for the preparation of solutions.
 
z

z
† 
z

It is known that the basis of majority of glass
†
z
 


 coatings is alkali-boron-aluminium glass, from which one
   z
 
† z
 
can obtain glass coatings with the assigned properties
†  
z
}
†
 †
 by certain combinations between some components. The
 
z } } z main problem is obtaining homogeneous multicomponent
glass-forming solutions based on water glass containing
.2 32
   
Al3+, B3+, P5+ ions. For their obtaining in the area of high
ðÍ sodium (M = 3-4), potassium (M = 3.5) and lithium
(M = 4-6) water glass, as well as aluminium and barium
Fig. 2. Composition of the synthesized nitrates, boric acid and ammonium hydrophosphate were
K2O-SiO2-P2O5 glass
used. The special difficulty of obtaining of homogeneous
Taking into account above-mentioned requirements, colloidal solutions based on water glass consists in the
we established the optimum composition of glass: P2O5 is fact that adding of even negligible quantity of salts of
within the range of 39-45 mol %, SiO2 – 8-15 mol %, elements of II and III groups to silicates solutions causes
K2O – 40-52 mol % (Fig. 2). However, the synthesized heterogeneity in such systems. The formation of insoluble
glass is characterized by low chemical stability and silicates of most metals is the main reason.
106 Yaroslav Vakhula et al.

SiO2 = 10 mol. % It should be noted that solutions based on potassium water

K2O= 30 mol. % glass with similar module are more stable. The increase
of stability is connected with higher ability to dissociation
of K+ ions.
Addition of even negligible quantity of aluminate
(V =0.5-1.0 ml) to 10 ml of water glass forms the spongy
admixtures on the boundary of liquids mixing. This
phenomenon was absent while introducing aluminate by
separate drops. Hence, for preparation of colloidal solution
the aluminate was added to water glass by small portions
Fig. 3. Composition of the synthesized under intensive stirring. Homogeneity of solution was
K2O-Al2O3-B2O3-SiO2-P2O5 glass saved only to the certain boundary amount of aluminate,
which, in the turn, depends on a kind of alkaline cation
We established that stability of colloidal solutions and module of water glass. At equal modules (M = 3) in
increases considerably, when Al+3+ ion is in anionic form solution of potassium and sodium water glass gelanization
as aluminate. The increase of aluminate content without begins after addition of 3 ml and 2 ml of aluminate,
sediment formation is limited to boundary amount. The correspondingly. The effect of alkaline silicate module is
increase of sodium water glass module from 3 to 4 more considerable. At increase of module to 4 gel is formed
decreases aluminate boundary amount almost in 2.5 times. when adding 1 ml of aluminate (vide Table 3).
Table 3
Boundary amounts of Al2O3 in solutions based on water glass
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We determined aluminate boundary amounts and
re-calculated Al2O3 amounts, which may be added to the
solution of water glass without gelanization.
If there are not difficulties in obtaining of sodium
and potassium water glass of wide module intervals, the
synthesis of lithium water glass with the module M>2 has
some peculiarities. Literary information on this question
is limited. Lithium water glass (LWG) with M>2 is
heterophase system which consists of solution of lithium
silicate and suspended particles of polymerized SiO2 with
OH-groups on a surface. The increase of LWG module
from 2 to 10 increases content of suspended particles.
For LWG synthesis the optimal temperature of LiOH
solution is 323-348 K. The rise in temperature results in
LWG hydrolysis and increases number of suspended
particles. Weak LiOH solutions (c = 0.1-0.5 N) lead to
intensive interaction between components and decrease
size of particles. Strong LiOH solutions (c = 1.5 N)
increase number of suspended particles up to formation
of high-viscous LWG solution. Thus, an amount and size
of suspended particles depend upon the module of water
glass, temperature, synthesis time and LiOH concentration.
Taking into account the fact that concentration of
colloidal solutions is one of effective factors during their
stabilization, we diluted synthesized lithium-potassium
water glass with water till the concentration became 6.5
mass %.
The general scheme of components confluence is
given below:
K2O×3.5SiO2 + Li2O×4SiO2 + LiOH + Al(NO3)3 +
+H3BO3 + Ba(NO3)2
The gelanization depends on chemical composition
of solutions and it becomescomplicated at availability of
two or more glass-formers.
We established that in solutions of potassium-
silicium-phosphate system there is deviation from the
established regularities of gel-forming process in the
different interval of pH. In particular, in the area of pH<6
solutions do not increase their stability, but it takes place
in silicates solutions. The introduction of phosphatic
component into gel structure was confirmed by a chemical
analysis. Maximal amount of P2O5 is introduced actually
at pH = 4, that considerably adjusts the existent gel-forming
theory of silicates aqueous solutions and allows to
understand essence of such rejection. Introduction of
phosphatic component into gel structure is explained with
high charge of phosphate-ions and their inclination to be
adsorbed on the surface of porous gel.
The decrease of concentration of colloidal solution
decreases the number of SiO2 collisions. Moreover, the
increase of number of hydroxyl ions results in
depolymerization of phosphatic and silicium-containing
chains, which in general increases the gelanization time.
 Peculiarities of Formation of Sol-gel Coatings Based on Water Glass 107

The effect of temperature on gelanization time is
complicated. The minimum value of time is observed at
333 K. It is possible to assert that decrease of viscosity at
mentioned temperature interval decreases the number of
colloidal particles sharply and decelerate the aggregation
process.
For the preparation of solutions of K2O–Al2O3–
B2O3–SiO2–P2O5 system potassium water glass (M=3.5;
c=14.47 mass %), KOH (9M), (NH4)2HPO4 (1.5M), H3BO3
(0.7M) solutions were used. The general concentration
of colloidal solution was 17.7 mass % and pH was 9.1.
The solutions of this system have high ability to
gelanization, which is especially sensible to the value of
concentration of hydrogen ions. We established
experimentally that a sharp change in the behavior of
solutions is observed in the area of pH = 10. That is why
it is important in every case to establish the characteristic
features of solutions preparation. At the obtaining of solution
with pH < 10 order of components confluence is the
following:
(NH4)2HPO4 + H3BO3 + KOH + K2O×3.5 SiO2 +
+Kn[Al(OH)m]
At the obtaining of colloidal solution of investigated
system with pH > 10 according to mentioned scheme,
insoluble sediment is precipitated after the adjustment of
(NH4)2HPO4 + H3BO3 mixture with ammoniac water. In this
connection there is a necessity to change order of
component confluence:
Kn[Al(OH)m] + KOH +K2O×3.5SiO2 +(H3BO 3 +
+(NH4)2HPO4)

Table 4
Physical and chemical properties of protective glass coating

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Table 5
Physical and chemical properties of glass-ceramic insulating coating
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108 Yaroslav Vakhula et al.

Table 6
Physical and chemical properties of decorative glass coating

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3. Conclusions
1. For the obtaining of functional coatings in the
R2O-SiO2 (R – Li,Na,K) system the complex of chemical
compositions is developed by large-scale modification of
the system with MgO, CaO, BaO, B2O3, Al2O3, P2O5 oxides
with the purpose of achieving such necessary technological
characteristics of coating as coefficient of linear expansion,
chemical and thermal stability, forming viscosity and
crystallization ability. We developed glass coatings with
the following functional properties: Li2O and Na2O have
protective temperaturestable properties, Li2O + K2O –
insulating properties and K2O – fusible decorative ones.
2. Compositions of stable to gelanization solutions
on the basis of R2O×nSiO2 water glass were developed.
Peculiarity and difficulty of preparation is related to
formation of sparingly soluble salts of silicium acid. We
established that stability of colloidal solutions increases
considerably, when Al3+ ion is in anionic form as aluminate.
The increase of aluminate amount without sediment
formation is possible only to the certain boundary amount.
The increase of sodium water glass module from 3 to 4
decreases aluminate boundary amount almost in 2.5 times.
Solutions based on potassium water glass with similar
module are more stable, what is related to the greater ability
of K+ ions to dissociation. There is chemical interaction
 ZLWKRXWFKDQJHV
between components during the solution preparation. As
a result, system of pH is changed, which leads to
gelatinization or sedimentation.
References
[1] Atkarskaya A.: Steklo i keramika, 1997, 10, 14.
[2] Shevchenko V.: Physika I khimiya stekla, 1990, 16, 577.
[3] Ailer R. Khimiya kremnezema. Moskwa, 1982.
[4] Sujkovskaya N. Khimicheskie metody polucheniya tonkih
prozrachnyh plenok. Leningrad, 1971.
[5] Kuznecova L., Golubeva T., Hashkovskyi S. and Belustin
A.: Jurnal prikladnoi khimii, 1998, 71, 553.
ÎÑÎÁËÈÂÎÑÒ² ÔÎÐÌÓÂÀÍÍß ÇÎËÜ-ÃÅËÜ
ÏÎÊÐÈÒÜ ÍÀ ÎÑÍβ вÄÊÎÃÎ ÑÊËÀ
Àíîòàö³ÿ.  ðîáîò³ ðîçãëÿíóòî îäåðæàííÿ êîìïîçèö³é
äëÿ çàõèñíîãî, ³çîëÿö³éíîãî ³ äåêîðàòèâíîãî ïîêðèòòÿ, à
òàêîæ ôîðìóâàííÿ ïîêðèòü ç âèêîðèñòàííÿì çîëü-ãåëü
òåõíîëî㳿. Âèçíà÷åí³ îñíîâí³ óìîâè, íåîáõ³äí³ äëÿ
ïðèãîòóâàííÿ ãîìîãåííèõ êîëî¿äíèõ ðîç÷èí³â äëÿ ôîðìóâàííÿ
ïîêðèòü, à òàêîæ ¿õ îñíîâí³ õàðàêòåðèñòèêè. Ïðèâåäåí³
îñîáëèâîññò³ ôîðìóâàííÿ çîëü-ãåëü ïîêðèòü íà îñíîâ³ ð³äêîãî
ñêëà.
Êëþ÷îâ³ ñëîâà: çîëü-ãåëü òåõíîëîã³ÿ, ñêëîïîêðèòòÿ,
êîëî¿äíèé ðîç÷èí, ð³äêå ñêëî
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 1, No. 2, 2007 Chemical technology

Sergey Boychenko, Oksana Vovk, Larisa Chernyak and Ksenya Akinina

QUALITY AND ECOLOGICAL SAFETY OF MOTOR FUELS

National viation University, Kyiv
chemmotology@ukr.net; test@nau.edu.ua
Received: March 30, 2007

Abstract. Article considering interconnection of fuel
quality for transport and ecological safety. Main directions
were offered of solving ecological-energy problem system
"human-environment-fuel-transport".
Key words: fuel, transport, ecological safety, ecological
properties.
Energy ecological problems and aspects of its
rational development are very urgent today (Fig. 1).

 



Fig. 1. Harmful substances emission balance during
transport exploitation:
1 - automobile transport (70 %); 2 - agricultural (9.4 %);
3 - railway (9.2 %); 4 - air (7.3 %); 5 - water (4.1 %)
Fuel for transport engines is well-known toxically
harmful substances, which can cause industrial injury,
diseases or health problems of people who work in specific
area. Environment pollution by oil products is caused by
its evaporation or leakage and fuel combustion emissions
into atmosphere during engine working.
High atmospheric air quality providing is one of
the most important aspects. Ukraine with other
industrialized countries signed and performs Montreal
protocol (1988) about ozone depletion protection,
Convention of Organization of United Nations at New-
York (1992) about climate change and Kiyoto Protocol
(1997), which assigned decreasing of harmful substances
emissions to the whole country and separately to each
branch of economy, where energy is individual part. The
main goal is to prevent global consequences from carbon
dioxide and other emissions, which cause ozone
depletion.
Requirements for harmful substances emissions
regulate by rule 49 ÅEC ÎUN and directive 88/77 ÅU
(Tables 1-3).

Table 1
Regulations for transport ecological compatibility

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110 Sergey Boychenko et al.

Table 2
Regulations dynamic for automobile toxicity

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Table 3
Regulations dynamic for diesel automobile toxicity

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USA selected strategic direction in reformulated petrol application of reformulated petrol - California Air Resources
producing for increasing of petrol ecological characteristics. Board (CARB-I, CARB-II). Comparison of USA petrol quality
California State developed hardwired production and indexes with European indexes is in the Table 4.

Table 4
Petrol quality indexes comparison

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European countries from the year 2000 according to EN 228 specified benzol content decreasing
implemented new specification on automobile petrol's. from 5.0 to 1.0 rel. %, and total aromatic hydrocarbons
Ecological requirements to European automobile petrol from 42.0 to 30.0 rel. %.
 Quality and Ecological Safety of Motor Fuels 111

Table 5
Physical-chemical petrol indexes comparison
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Table 6
Ecological requirements for petrol (Directive of European Union 2003/17/ÅU)
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112 Sergey Boychenko et al.

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Ecological requirements for diesel fuel (Directives of European Union 2003/17/ÅU)
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These requirements reflected in european standards
of series Euro-2, 3, 4, 5 (Tables 1-3), requirements of
World Charter of fuel producers (Table 5) and Directive
of European Union 2003/17/ÅU (instead of Directive 98/
70/ÅU), assigned ecological requirements to fuels
(Tables 6. 7).
Automobile transport development perspectives are
very broad, which indicates level of anthropogenic
influence increasing on atmospheric air purity, flora and
fauna.
Diesel fuel producing and consumption is increasing
with parallel automobile petrol large volume producing.
Diesel transport is one of the main sources of environmental
pollution by sulfur oxides, nitrogen, soot particles and
toxic aromatic hydrocarbons.
On December'2000 directive of Management on
environmental protection USA (ÅÐÀ) was published,
according to directive requirements from June'2006
sulphur content in diesel fuel should not be more then
0.0015 % mass.
European Union standard ÅN 590, which decreases
sulfur content from 0.2 % to 0.005 %, is an example of
ecological requirements toughen as to diesel fuels. None
of technical decisions accepted without thorough
ecological expertise.
 
 
Aviation transport increasing in transport complex
system of developed countries economy. For example,
in 1970 USA aviation transport consumed 7.5% of energy,
which used by transport sector. In 1985 energy consump-
tion by aviation increased up to 27 %, in 2000 – to 32.5%.
Amount of air planes (AP) is rising up. In 1970 world AP
park counted 7301 planes, but today there are more then
8000. Subsonic aircraft contains 90 %, rest 10 % –
supersonic AP. During the 1990 to 1995 world park of
civil AP increased from 357.5 thousands aircrafts to 369.1
thousands, on 3 %.
Forecast International published information that
in 2004-2013 more then 5835 huge civil and transport
airplanes will be build in the world. According to World
Airfleet data there are about 2 thousands air companies,
which have 50 thousand aircrafts.
Administrative aviation develops lately and aviation
of business class. According to National association of
administrative aviation of USA data in 1990 World Park of
certain class AP had 14727 airplanes, 6728 airplanes with
turbojet engine.
Aviation engine fuel production is one of the most
developing branches in oil refining industry of the world
(Table 8).
 Quality and Ecological Safety of Motor Fuels 113

Table 8
Fuel quality indexes comparison of jet fuels of different countries-producers
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114 Sergey Boychenko et al.
Automobile emissions contain more then two
hundred types of toxic elements, such as: carbon oxide,
nitrogen, sulfur, heavy metals, carcinogens and mutagens,
hydrocarbons, aldehyde, aerosols, sulfurous anhydride,
etc. (Table 9). Every year automobile imbibe 4350 kg of
oxygen from atmosphere, and emitted 3250 kg of carbon
and 530 kg carbon monoxide, 90-150 kg unburnt
hydrocarbon, 40 kg nitrogen oxide, up to 1 kg of lead.
Also 96 % carbon oxide, 30 % nitrogen oxide, 68 %
hydrocarbons are emitted into atmosphere through exhaust
pipe of automobile. Wrong exploitation of transport can
be the reason for toxic substances emission increasing
ÑÎ, ÑnÍm – up to 25–30 %, NOx – up to 15 %.
Table 9
Specific loss of petrol and diesel engine
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Intensity of harmful substances emissions by one
diesel locomotive is an analog to 15-20 trucks or 40-60
automobiles. One aircraft ÒU-154 during take off and landings
is emitting into the atmosphere 100 times more harmful
substances then car. 2-4 mg/min of carcinogenic substances
(benzopiren) is emitted into atmosphere during the work of
turbo jet and turboprop engines. Air plane is emitting 3.7 t
carbon oxide, 2 t hydrocarbons (unburned fuel) and 1.7 t
nitrogen oxide per day by take offs and landings.
In 1985 world aviation emitted into atmosphere
more then 1.2 (100) mln. tones of ÑO, 0.8 (25) mln.
tones ÑH, 1.4 (15) mln. tones NO.
The main danger of harmful substances is its
emissions at cites, streets, parking lots, airports where
contain in bottom layer on the level of human respiratory
organs. Fuel evaporation is dangerous and poisonous; it
can cause harm for human, plants and animals. When air
saturated with petrol evaporations is inhaled in amount of
5-10 mg/l, acute poisoning reaches human organism.
Harmful substances formation conditions, which is
contained in transport engine exhaust gas described in
details in special literature.
Hydrocarbons are the most harmful substance,
which pollute atmosphere and have dangerous impact on
human. Hydrocarbons are indicators of carburetion and
combustion process poor organization or major lack of
air in engine fuel mixture. Fuel combustion products
contain various hydrocarbons: methane ÑÍ4, ethane Ñ2Í6,
propane Ñ3Í8, acetylene Ñ2Í2, ethylene Ñ2Í4, benzol Ñ6Í6,
toluol Ñ6Í5ÑÍ3 etc. Hydrocarbons enter to photochemical
reaction with nitrogen oxides under the influence of the
sun, produce wide spectrum of substances (peroxide,
ozone etc.), which accelerate corrosion of different
materials, harmful for plants, and one of the reason of
smog formation, which causes lungs diseases. Ozone is
the most dangerous among photo oxides. When
concentration is 200 mkg/m3 it is causes irritation of eyes,
nose mucosa and headache. Exhaust gas hydrocarbons
has carcinogenic influence on human organism. Benzopiren
has biological influence (ÁàÏ, 3,4-benzopiren, C22H14).
Tetraethyl lead (TEL) (Ñ2Í5)4Pb and tetra methyl
lead (TML) (ÑÍ3)4Pb are very toxic components, used
for petrol octane number increasing contains lead. For
removing of combustive products effluxes are used (lower
bromide, chloride); decrease lead content in 3-5 times in
combustive chamber. It means that 90-98 % of lead
contained in ethyl petrol is emitted in atmosphere. Lead
forms aerosols with automobile gases, which absorbed
by lungs with air and stored with food and water in stomach
and causes disorder central nervous system, fainting, injury
of liver, kidney, decreasing of vision, genetic disfunction.
Because of definite element toxicity most countries forbid
its content in petrol's and require automobile exploitation
on non-ethylene petrol.
Another reason of atmosphere contamination - is
fuel evaporation during transportation, storage,
technological discharge operations, loading, refueling and
from transport fuel systems. From all types of losses this
one have class "irretrievable", part of them protected and
regulated by oil products losses (kg/t) according to
“Norms of oil products natural loss during storage,
distribution and transportation” reflects natural loss of
various types of oil products in different technological
operations. When consumption of oil products increasing,
damage to economy and ecosystem also increasing in the
result of natural losses. Small dirt part (list of them contain
viewed emissions) is huge in conditions of anthropogenic
atmospheric pollution and depletion of Earth “protective
shield” – ozone layer. Ozone decreasing is registered today
and theoretical model analysis help scientists to predict
changes of ozone in the nearest years by given
concentration changes of various harmful substances from
anthropogenic sources. Inherent decreasing of ozone layer
(up to 10 % and more) is real in the nearest 15-30 years,
because of emissions increasing. According to
Environmental protection International committee data
ozone holes are located above every city, and above
Antarctica the hole has diameter of 8 km.
To realize statements of Kiyoto protocol and used
article 2 (iv and vii, IPCC method) we have done
calculation of greenhouse gases into equivalent of ÑÎ2.
Initial data is daily emissions from regular refueling station
in amount of 60 kg particular volatility organic compounds
 Quality and Ecological Safety of Motor Fuels
(VOC); we have to consider potential of global warming
defined by 100 years term. Emissions on such term are
2160000 kg. Transferring of received amount of VOC
into CO2 (in regard to potential of global warming indexes
for ÑÍ4, that at UNFCCC evaluation is 23) we got 0.00506
Tg equivalents to ÑÎ2.
Conclusion
Analysis mentioned above shows to solve
ecologically energetic problems of energy, connected with
transport exploitation and motor fuel application, optimal
complex approach applied to system "human –
environment – fuel – transport", granting all technological
chains specifications from the moment of oil extraction
to product transformation of unburnt gases and fuel.
Main directions of ecologically energetic problem
solving of system "human – environment – fuel –
transport" are: 1) motor fuel quality increasing with
ecologically safe characteristics; 2) engine construction
115
improvement with purpose of combustion efficiency and
harmful substances emission transformation in unburnt
gases increasing; 3) alternative fuels application; 4) envi-
ronmental procedures on the object of oil products
complexes, system of transportation, refueling stations,
petroleum storage depot; 5) organizational procedures
including harsh regulations (standards), which control
harmful substances emissions in unburnt gases and volatile
hydrocarbons, which evaporate into atmosphere.
ßʲÑÒÜ ² ÅÊÎËÎò×ÍÀ ÁÅÇÏÅÊÀ ÏÀËÈÂ
ÄËß ÒÐÀÍÑÏÎÐÒÍÈÕ ÇÀÑÎÁ²Â
Àíîòàö³ÿ. Ó ñòàòò³ ðîçãëÿíóòî âçàºìîçâÿçîê ÿêîñò³
ïàëèâ äëÿ òðàíñïîðòíèõ çàñîá³â òà åêîëîã³÷íî¿ áåçïåêè.
Çàïðîïîíîâàíî ãîëîâí³ íàïðÿìêè âèð³øåííÿ ýêîëîãî-
åíåðãåòè÷íèõ ïðîáëåì ñèñòåìè "÷îëîâ³ê – íàâêîëèøíº
ñåðåäîâèùå – ïàëèâî – òðàíñïîðòíèé çàñ³á".
Êëþ÷îâ³ ñëîâà: ïàëèâî, òðàíñïîðòí³ çàñîáè, åêîëîã³÷íà
áåçïåêà, åêîëîã³÷í³ âëàñòèâîñò³.
 INSTRUCTIONS TO AUTHORS
Manuscripts of the articles should be addressed to the Editor-in-
Chief
Prof. Michael Bratychak
Lviv Polytechnic National University
12, Bandera str, 79013 Lviv
and via e-mail: mbratych@polynet.lviv.ua
General
The content of the manuscripts must correspond to the scope of
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technology as:
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minerals;
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productions;
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Authors are fully responsible for the content of their published
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Note for Ukrainian authors. Presence of expert conclusion (the
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article is obligatory.
After the review of the manuscript page proofs are sent to the
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Manuscripts have to be submitted in 2 copies in Microsoft Word
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I
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 Lviv Polytechnic National University
Department of Chemical Technology of Oil and Gas Refining

invite specialists for

IV Scientific-Technical Conference
“Advance in
Petroleum and Gas Industry and Petrochemistry”
September 11–14, 2007
(in the main building of Lviv Polytechnic National University, 12, Bandery str.
and at the Department of Chemical Technology of Oil and Gas Refining, 2, St.Yura sq.)

TOPICS:

· Oil and Gas Processing

· Petrochemistry and Coal Chemistry
· Himmotology of Lubricants and Technical Liquids
· Organic Synthesis Products, Polymers and Compositions
· Ecology

Address for correspondence:

Lviv Polytechnic National University,
12, Bandery str., 79013, Lviv, Ukraine
e-mail: mbratych@polynet.lviv.ua