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Volume 2 ? Number 1

LITTERIS ET ARTIBVS

Lviv Polytechnic
2008 National University
 CONTENTS

Chemistry

Volodymyr Dibrivny, Yurij Van-Chin-Syan and Galyna Melnyk

Thermodynamic properties of sili con containing acetylene peroxides 1
Iryna Yevchuk, Roman Makitra, Olena Pal’chykova and Galyna Khovanets’
Regularities of organi c solvents diffusion into fluoropolymer structure 7
Volodymyr Donchak and Khrystyna Harhay
Synthesis of fluorinated polystyrene 11
Zoubida Seghier, Ambroise Diby, Vanda Voytekunas, Philip Cheang and Marc J.M. Abadie
Effect of filler type, content and size on the UV-curing dental materials 15
Arnold Karateev, Andrew Koryagin, Denis Litvinov, Ludmila Sumtsova and Yana Taranukha
New network polymers based on furfurylglycidyl ether 19
Witold Brostow and Tea Datashvili
Chemical modification and characterization of boehmite particles 27
Evgeniy Davydov, Georgiy Pariiskii, Iryna Gaponova, Tatyana Pokholok, Gennady Zaikov
Polymers in polluted atmosphere. Free radical and ion-radi cal conversions initiated
by nitrogen oxides 33

Chemical Technology

Oleg Grynyshyn, Michael Bratychak, Volodymyr Krynytskiy and Volodymyr Donchak

Petroleum resins for bitumens modifi cation 47
Vyacheslav Zhyznevskiy and Volodymyr Gumenetskiy
Catalytic oxidation of tert-butyl alcohol to methacrolein 55
Anatoliy Starovoit and Yevgen Maliy
Research of polymeric additive influence of organic composition
on thermochemical conversion of carbon masses 65

History

Tamara Perekupko, Yaroslav Kalymon and Kostyantyn Blazhivsky

Department of chemistry and technology of inorganic substances: the past, the present, the future I

Current Events

J. Pielichowski, R. Kozlowski, G. Zaikov and L. Madyuskina

IXth International conference on frontiers of polymers and advanced materials VII
Gennady Zaikov and Marina Artsis
XXXI International vacuum mi crobalance techniques conference XI
Gennady Zaikov and Marina Artsis
First International conference on biodegradable polymers and sustainable composites XIII

iii
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 1, 2008
Volodymyr Dibrivny, Yurij Van-Chin-Syan and Galyna Melnyk
THERMODYNAMIC PROPERTIES OF SILICON CONTAINING
ACETYLENE PEROXIDES
Lviv Polytechnic National University,
12 Bandera str., 79013 Lviv, Ukraine
vtchaiko@txnet.com
Received: May 24, 2007
Abstract. A technique for the explosion combustion of
liquid organosilicon peroxides has been developed. Five
silicon containing acetylene peroxides have been
investigated thermodynamically. Their combustion and
evaporation enthalpies have been determined. Formation
enthalpies of the compounds concerned in the condensed
and gaseous states have been calculated. The magnitudes
of two fragments for Benson additive scheme of formation
enthalpies have been determined.
Key words: organosilicon peroxides, evaporation enthalpy,
formation enthalpy, saturated vapour pressure, fragment
for Benson additive scheme.
1. Introduction
Organosilicon peroxides possess the whole range
of valuable properties. Their high thermal stability,
hydrophobic qualities, hydrolytic, and storage stabilities
have to be mentioned separately. Various free-radical
processes, such as vulcanization of elastomers, high
temperature (420–570 Ê) initiation of polymerization,
polymers modification, and varnish compositions curing
[1] are the major fields the above mentioned compounds
are used. In addition to that, film-forming abilities,
antioxidant properties, and biological activity of the silicon
containing acetylene peroxides are being investigated [2].
Absence of the thermodynamic properties of the
mentioned compounds complicates the processes of their
synthesis and inculcation.
The results of the experimental determination of
the formation enthalpies of the five liquid silicon containing
acetylene peroxides in the condensed and gaseous states
are represented in this article. The following five
compounds had been the subjects of the investigation:
3-methyl-3-tert-butylperoxy-1-trimethylsilyl-1-butyn (I)
(CH3)3COOC(CH3)2C { CSi(CH3)3
3-methyl-3-tert-amylperoxy-1-trimethylsilyl-1-butyn (II)
CH3CH2(CH3)2COOC(CH3)2C { CSi(CH3)3
Chemistry
3-methyl-3-tert-hexylperoxy-1-trimethylsilyl-1-butyn (III)
CH3(CH2)2(CH3)2COOC(CH3)2C { CSi(CH3)3
3-methyl-3-[2-cyclohexylpropylperoxy]-1-trimethylsilyl-1-butyn(IV)
cyclo–C6H11(CH3)2COOC(CH3)2C { CSi(CH3)3
dimethyldi[3-methyl-3-tert-amylperoxy-1-butynyl]silan (V)
[CH3CH2(CH3)2COOC(CH3)2C { C]2Si(CH3)2
2. Experimental
2.1. Synthesis
Samples of the studied peroxides have been
synthesized according to the procedure [3]. All the
compounds have been purified by vacuum distillation. The
products have been identified by infrared spectroscopy
(spectrometer UR-20), nuclear magnetic resonance
spectroscopy (spectrometer Tesla BS-567A), and ultraviolet
spectroscopy (spectrometer Specord UV-Vis). The contents
of carbon, silicon, and hydrogen have been established using
an element analysis. The content of active oxygen has been
estimated by the iodine method. The molecular masses of
the samples have been obtained by the cryoscopy method.
2.2. Purity
The purity of the compounds has been measured
by high pressure solution chromatography method. A
device for measuring the purity of the compounds
consisted of the pump, ultraviolet and refractometric
detectors and Separon SGX CN column. Eluent: a mixture
of heptan-isopropanol (98:2 volume parts ratio). The
content of the major component has been not less than
99.2 % for all the studied compounds. The thermal
properties of the peroxides have been studied at the Paulik-
Paulik-Erday derivatograph. Maximum destruction
temperature has been 430–440 K.
2.3. The sublimation enthalpies
The vapor pressure of the silicon containing
acetylene peroxides has been measured by integral effusion
Knudsen method. A stainless steel chamber with the
2 Volodymyr Dibrivny et al.
following parameters has been utilized in the experiments:
10 mm diameter, 20 mm height, 1 mm wall thickness.
Two membranes made of 0.05 mm thick nickel foil have
been used. The diameters of the effusion apertures have
been 0.5903 mm and 0.3247 mm. The design of the
experimental device has been taken from [4]. The
experimental techniques have been chosen based on the
recommendations [5].
The reliability of the device functioning has been
proved by measuring benzoic acid vapour pressure in the
temperature interval of 318–348 K. The results of the
measuring have been processed using the least-squares
method with the Studentized confidence coefficient of 95
per cent and represented as a set of linear equations:
lnPC=(34.8±0.4)-(111.1±1.3)´102T-1 (1)
For the membranes with 0.5903 mm apertures.
lnPC=(35.0±0.5)-(111.5±1.5)´102T-1 (2)
For the membranes with 0.3247 mm apertures
The sublimation enthalpies have been calculated
according to equations (1) and (2) and equal 92.4±1.1
and 92.7 ±1.3 kJ×mol-1 respectively. These values are within
experimental error and are consistent with those previously
published [6].
The saturated vapour pressure of the benzoic acid
has been calculated by extrapolation of the values of the
vapour pressure inside the chamber with different aperture
diameters to zero diameter [7]. Adjustment multipliers for
membranes with the diameters of 0.3247 mm and
0.5903 mm equal 1.04 and 1.14 respectively. These
coefficients have been later used for calculation of saturated
vapour pressure of silicon containing acetylene peroxides.
A series of 7 to 15 experiments have been conduc-
ted for every compound. The results of the experiments
could have been easily distorted by the presence of volatile
impurities. Therefore, the results of the experiments had
not been considered until the rate of evaporation became
constant (±1 per cent) under the predetermined
temperature. The error of the vapour pressure measuring
which can be brought by non-volatile impurities is less
than the measuring accuracy.
The mass of the effused compound Dm has been
determined by weighting of the effusion chamber with
the precision of ±5×10-6 g. The temperature of liquid
thermostat has been adjusted to an error of ±0.1 K. The
precision of measuring the temperature T and duration of
effusion t was ± 0.05 K and ±1 s respectively.
The results of the effusion measuring of the studied
peroxides including saturated vapour pressure P, and
vapour pressure inside the chamber PC, are presented in
Table 1.
Approximation equation coefficients of the
temperature dependencies of the saturated vapour pressure
lnP = A+B/T and average evaporation enthalpies DVH in
the investigated range of temperatures DT are presented
in Table 2. Here r is a correlation coefficient.
2.4. The combustion enthalpies
The combustion enthalpies of the silicon containing
acetylene peroxides have been measured by a water
calorimeter B-08 MA equipped with a isothermal (± 0.03 K)
jacket. Energy equivalent of the calorimetric system W
has been estimated by the combustion of the standard
benzoic acid with the content of the major component
being equal to 99.995 mol per cent, the estimation precision
being equal to ± 0.06 per cent.
The combustion heat of the benzoic acid allowing
for the Jessup factor was equal to 26426.9 J×g-1. The initial
pressure of the oxygen which has been previously cleaned
from the combustible impurities, carbon dioxide and water
was equal to 29.4×105 Pa. The initial temperature of the
main period in all experiments has been 298.15 K.
The choice of the combustion technique for the
liquid organosilicon peroxides has been made after
experimenting on the compound V. The combustion has
been held using a platinum or quartz crucible or a platinum
net. The maximum combustion completeness of the
compound V has been attained by using a platinum crucible
and has been equal to 99.1–99.8 per cent. Therefore, a
platinum crucible has been used for all other compounds
under study.
The samples have been isolated in double terylene
containers before the combustion. In addition to being an
isolation terylene has also been an auxiliary substance in
the combustion. It has enabled to attain simultaneous
ignition across the whole surface of the sample, increase
the temperature in the combustion zone, as well as to
ensure completeness of combustion and prevent formation
of a silicone carbide [8]. A cotton thread has been used
for the ignition of the samples.
A quantitative analysis of the combustion products
aimed at establishing the presence of carbon oxide, carbon
dioxide, soot, and nitric acid has been carried out after
every combustion. The quantity of the carbon dioxide has
been measured by the Rossini method [9] with the precision
of ±2×10-4 g. Reliability of the gas analysis has been proved
by the series of experiments with combustion of standard
benzoic acid. The content of carbon oxide in the
combustion products has not exceeded the precision of
the gas analysis. The amount of soot formed on the walls
of the platinum crucible has measured by weighting with
a precision of ±5×10-6 g.
Corrections for the combustion of the terylene
container (QC), the cotton thread (QTh), as well as for the
combustion of the soot to carbon dioxide (Q S), and
formation of the nitric acid (QA) have been made to
calculate combustion heats of the compounds. The
following combustion energies in the bomb conditions
(J×g-1) have been used in the calculations: terylene 22944.2
[10]; cotton thread 16704.2 [11]; soot to carbon dioxide
32800 [12]; formation of nitric acid 59 kJ×mol-1 [9]. The
 Thermodynamic Properties of Silicon Containing Acetylene Peroxides 3

Table 1
The results of the experimental determination of temperature dependencies of vapour pressure
of the studied peroxides

WV 'PJ   &3  3  WV 'PJ   &3  3 

3HUR[LGH, 3HUR[LGH,,,
         
         
         
         
         
         
         
     3HUR[LGH,9
         
         
         
         
         
         
3HUR[LGH,,     
         
     3HUR[LGH9
         
         
         
         
         
         
         
         
         
         
         
         
         

Table 2
Approximation equation coefficients of the temperature dependencies of the saturated vapour pressure
and evaporation enthalpies of the studied peroxides

3HUR[LGH '       USHUFHQW '9+N-˜PRO

, ± r r  r

,, ± r r  r

,,, ± r r  r

,9 ± r r  r

9 ± r r  r


4 Volodymyr Dibrivny et al.

Table 3
Results of the calorimetric determination of combustion energies of the studied peroxides
PJ ' 9 46- 47K- 4&- 4$- 46- N '8%-˜J
        
3HUR[LGH,: -˜9
        
        
        
        
        
        
        
3HUR[LGH,,: -˜9
      ²  
      ²  
      ²  
      ²  
        
        
        
        
        
        
        
3HUR[LGH,,,: -˜9H[S: -˜9H[S
        
        
      ²  
      ²  
        
        
3HUR[LGH,9: -˜9H[S: -˜9H[S
      ²  
        
        
        
        
        
        
        
3HUR[LGH9: -˜9
        
        
        
        
        
        
        

Table 4
Energies of combustion and enthalpy characteristics of the studied peroxides
3HUR[LGH ' 8 . S 'Q57 ' + . 'I+ . 'I+ JDV 'I+ JDV
OLTXLG H[S FDOF
 N-˜PRO 
, r   r r r 
,, r   r r r 
,,, r   r r r 
,9 r   r r r 
9 r   r r r 
 Thermodynamic Properties of Silicon Containing Acetylene Peroxides
quantity of the carbon dioxide which has formed from
the combustion of 1 g of terylene and the cotton thread is
2.2872 g and 1.6284 g respectively. The combustion
energies DU B determination results for the studied
peroxides are represented in Table 3. Here, m is a mass of
the initial sample; DT is an actual temperature rise; QS is a
total quantity of the emitted energy, k is combustion
completeness.
Calculation of standard combustion enthalpies
DCH0298.15 K of silicon containing acetylene peroxides has been
based on the combustion energy values of the peroxides
including Washburn correction p and correction for the
variation in the number of moles of gas DnRT. The calcula-
tion of formation enthalpies in condensed phase has been
based on the following key values of DfH0298.15 K, kJ×mol-1:
–285.830 ± 0.042 (H2O, liq.), –393.514 ± 0.046 (CO2,
gas) [13]; –939.39 ± 0.52 (SiO2, am. hydr.) [8].
The results of the calorimetric determination of
standard energies and enthalpies of combustion and
formation of silicon containing acetylene peroxides are
represented in Table 4. A standard deviation of average
values has been calculated taking into account the
Studentized confidence coefficient of 95 per cent.
3. Results and Discussion
Reaching a high degree of combustion
completeness is a major difficulty in determining a heat of
silicon containing peroxides formation heat. This problem
appears at the very beginning of the process; the first
portions of the newly formed silicone dioxide either envelop
or sorb the substance being burned, thus preventing
access for oxygen and combustion ceases [8].
As a result of burning of the studied organîsilicon
peroxides all inner surface of the bomb has been covered
with a silicon dioxide powder. This reconfirms that the
burning process included an explosion. Evidently, the
compound has dispersed into droplets during the
explosion. These droplets have burned out failing to reach
the cold walls of the bomb. The combustion completeness
of all the studied peroxides in all the experiments exceeded
99 per cent, which is considered to be sufficient for this
class of compounds.
To calculate formation enthalpies of silicon contai-
ning compounds from the enthalpies of their combustion
in oxygen, a reliable value of a standard formation enthalpy
of hydrated amorphous silicon dioxide is needed. The values
used up to now have ranged from –850.77 to
–939.39 kJ×mol-1 [8, 14-16]. We have chosen the value of
DfH0298.15 K (SiO2) to be equal –939.39 ±0.52 kJ×mol-1. It has
5
been obtained by direct combustion of the silicon (purity
equal to 99.999 per cent) [8] and reconfirmed by reaction
calorimetry [17].
The analysis of the obtained results (see Tables 2
and 4) shows that absolute values of the enthalpies of
evaporation and formation in liquid and gaseous phase
(kJ×mol-1) are increasing in the homologous series of
compounds I-III by 5, 21, and 15 respectively. The
contribution of C-(C)2(H)2 fragment in the listed above
enthalpy characteristics (kJ×mol-1) is 4.8 [7]; 24 [18] and
20 [19] respectively. Therefore, the values of the enthalpy
characteristics increase are equal to those of corresponding
enthalpies of C-(C)2(H)2 fragment within the precision of
determination. The differences between the fragments of
methyl and cyclohexyl groups (kJ×mol-1) for compounds I
and IV are equal: for gaseous phase formation enthalpies
–68.1 [19], for liquid phase formation enthalpies – 82.3
[18], and for evaporation enthalpies 25.1 [7]. These values
also correspond to the results of the experiments within
the precision of determination: –65, –86 and 20.7 kJ×mol-
1
respectively (see Tables 2 and 4). The obtained results
prove the additivity of enthalpy characteristics of the studied
silicon containing peroxides.
The studied compounds contain fragments whose
enthalpy characteristics have not been studied yet. That
is why, due to insufficient data fragments for calculation
of liquid phase formation enthalpies and evaporation
enthalpies can not be determined.
Gaseous phase formation enthalpies of the
fragments have been taken mostly from [19]. The
fragments O-(C)(O) – 19.32 kJ×mol-1 and C-(O)(C)2(Ct)
– 9.55 kJ×mol-1 have been taken from [20]. The first
fragment has been determined on the base of the formation
enthalpies of over fifty peroxides, the second one was
determined on the base of five compounds with a triple
bound. The value of C-(Si)(H)3 fragment (kJ×mol-1) can
be found in the following articles: [21] –44.27; [22-24]
–40.27; [25] –42.17. All the fragments of organosilicon
compounds have been recalculated [21-24]. Therefore,
we have chosen the value of –42.17 kJ×mol-1. It is equal
to the value of the fragment C-(C)(H)3 [19].
The system of four identic equations has been
derived by inclusion of the known fragments into the
equations of formation enthalpies of the compounds I –
IV. Solution of this system of equations has allowed to
calculate a group contribution (Ct) º CSi(C)3 which is
equal to 49 kJ×mol-1. The value of [(Ñt)ºÑ]2Si(Ñ)2 fragment
159 kJ×mol-1 has been determined from the formation
enthalpy of the compound V.
The calculated values of formation enthalpies belong
to the confidence interval of the experiment (Table 4).
6 Volodymyr Dibrivny et al.
4. Conclusions
The magnitudes of two fragments for Benson
additive scheme allow calculate the formation enthalpies
of silicon compounds, which contain determined
fragments.
The obtained base thermodynamic characteristics
of organosilicon peroxides can be used for optimization
of existing and creation of new technologies of synthesis
and purification of elementorganic peroxides.
References
[1] Fomin V.: X International Conference on Chemistry of
Organic and Elementorganic Peroxides, Moscow, 1998, D5.
[2] Agabekov V.: IX All-Union Conference on Chemistry of
Organic Peroxides, Gorkij, 1990, 8.
[3] Yuvchenko A., Dikusar E. and Zhukovskaya N.: Zh.
Obshch. Khim., 1993, 63, 143.
[4] Ribeiro da Silva A. and Monte J.: Thermochimica Acta,
1990, 171, 169.
[5] Krasulin A., Kozyro A. and Kabo G.: Zh. Prikl. Khim., 1987,
6, 104.
[6] Kruif G. and Blok J.: J.Chem. Thermodyn., 1982, 14, 201.
[7] Lebedev Yu. and Miroshnichenko E.: Termokhimiya
obrazovaniya parov organicheskih veshchestv. Nauka,
Moskva 1981.
[8] Voronkov M., Klyuchnikov V., Danilova T. and Korcha-
gina A.: Izvestia Akad. Nauk SSSR. Ser. Khim., 1986, 9, 1970.
[9] Rossini F. (ed.): Experimental Thermochemistry.
Interscience Publishers Inc., N.Y., London 1956, v.2.
[10] Pimenova S.: PhD thesis, Moscow 1981.
[11] Kornilov A., Lebedev O. and Skuratov S.: Zh. Phys. Khim.,
1964, 38, 2013.
[12] Popov M.: Termometriya i kalorimetriya. Moscow State
University, Moscow 1954.
[13] CODATA Recommended key values for thermodynamics
1977, J. Chem. Thermodyn., 1978, 10, 903.
[14] Tanaka T., Takahashi U., Okawara R. and Watase T.:
J. Chem. Phys., 1951, 19, 1330.
[15] Good W., Lacina J., De Prater B. and Micullough J.:
J. Phys. Chem., 1964, 68, 579.
[16] Bell N., Perkins A. and Perkins G.: J. Chem. Faraday Trans.,
1981, 77, 1779.
[17] Voronkov M., Baryshok V., Klyuchnikov V., Korchagina
A. and Pepekin V.: J. Organomet. Chem., 1989, 359, 169.
[18] Kizin A., Dvorkin P., Rygova G. and Lebedev Yu.: Izvestia
Akad. Nauk SSSR. Ser. Khim., 1986, 2, 372.
[19] Benson S.: Thermochemical Kinetics. John Wiley & Sons,
Inc., New York-London-Sydney 1971.
[20] Van-Chin-Syan Yu.: D. thesis, Moscow 1986.
[21] Voronkov M., Sorokin M., Klyuchnikov V., Shvetz G. and
Pepekin V.: J. Organomet. Chem., 1989, 359, 301.
[22] Voronkov M., Klyuchnikov V., Sokolova E. and Danilo-
va T.: J. Organomet. Chem., 1991, 401, 245.
[23] Voronkov M., Klyuchnikov V., Mironenko E., Shvetz G.
et al: J. Organomet. Chem., 1991, 406, 91.
[24] Voronkov M.G., Klyuchnikov V.A., Marenkova E.V.,
Danilova T.F. et al: J. Organomet. Chem., 1991, 406, 99.
[25] Mosin A.: Zh. Phys. Khim.: 1976, 50, 866.
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ÊÐÅÌͲÉÂ̲ÑÍÈÕ ÀÖÅÒÈËÅÍÎÂÈÕ ÏÅÐÎÊÑÈIJÂ
Àíîòàö³ÿ. Ðîçðîáëåíî ìåòîäèêó ñïàëþâàííÿ ð³äêèõ
êðåìí³éîðãàí³÷íèõ ïåðîêñèä³â ³ç âèáóõîì. Òåðìîäèíàì³÷íî
äîñë³äæåí³ ï‘ÿòü êðåìí³éâì³ñíèõ àöåòèëåíîâèõ ïåðîêñèä³â:
âèçíà÷åí³ åíòàëüﳿ çãîðÿííÿ òà âèïàðîâóâàííÿ. Ðîçðàõîâàí³
åíòàëüﳿ óòâîðåííÿ ñïîëóê â ð³äêîìó ³ ãàçîïîä³áíîìó ñòàí³.
Ðîçðàõîâàí³ äâà ôðàãìåíòè äî àäèòèâíî¿ ñõåìè Áåíñîíà äëÿ
âèçíà÷åííÿ åíòàëüï³é óòâîðåííÿ.
Êëþ÷îâ³ ñëîâà: êðåìí³éîðãàí³÷í³ ïåðîêñèäè, åíòàëüï³ÿ
âèïàðîâóâàííÿ, åíòàëüï³ÿ óòâîðåííÿ, òèñê íàñè÷åíî¿ ïàðè,
ôðàãìåíò àäèòèâíî¿ ñõåìè Áåíñîíà.
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 2, No. 1, 2008 Chemistry

Iryna Yevchuk1, Roman Makitra2, Olena Pal’chykova2 and Galyna Khovanets’1

REGULARITIES OF ORGANIC SOLVENTS DIFFUSION INTO

FLUOROPOLYMER STRUCTURE
Department of Physical Chemistry of Combustible Minerals,
1 

L.M. Lytvynenko Institute of Physico-Organic Chemistry and Coal Chemistry NAS of Ukraine
3 Naukova str., 79053 Lviv, Ukraine; vfh@org.lviv.net
2
Institute of Geology and Geochemistry of Combustible Minerals NAS of Ukraine
3 Naukova str., 79053 Lviv, Ukraine
Received: January 11, 2008

Abstract. Diffusion coefficients of organic solvents into
tetrafluoroethylene-propylene copolymer structure may be
generalized by multiparameter equations. Molar volume
and cohesion energy of penetrating liquids are suggested
to be determining their values and retarding the process.
Keywords: multiparameter equation, diffusion coefficient,
swelling.
We have made an assumption that in the diffusion
processes both molecules’ sizes and their solvation
interactions ability are significant. Simultaneous consideration
of all these factors is possible by employing the free energies
linearity concept by means of linear multiparameter equations.
The authors [4, 5] show that in case of low-polarity polymers
(cis-isoprene, butadiene-styrene etc.) relation between
diffusion coefficient and penetrants’ properties is satisfactorily
described by equation (1):

1. Introduction
Process of diffusion of organic solvents into polymer
structure is of both theoretical and practical interest,
especially in view of membrane technologies development.
That is why a great number of investigations are devoted
to it [1]. However, unlike diffusion in homogeneous medium
which complies with Fick, Einstein-Stocks and other
equations, the problem of relation between diffusion rate
of a penetrant into polymer structure and its properties has
not been solved till now [2]. For instance, in case of diffusion
into polymer membranes numerous deviations from the
known expression Qt / Q¥ = ktn a are noted (where Qt is
the amount of solvent absorbed during the time t, Q¥ is the
same value at saturation, k and n are constants.) At n = 0.5
the process complies with Fick law, however, as a rule,
n > 0.5, which implies that the process occurs in the field
of so called anomalous transport. When considering this
problem from the position of the theory of regular solvents,
the suggested relation between the characteristics of swelling
and diffusion processes and the Hildebrand solubility
parameter d has only semiquantitative character since it
does not take into account the effect of possible specific
interactions. The attempts to describe the diffusion via molar
volume of liquid Vì failed too. Although according to the
Einstein-Stocks formula D = kT/6phr diffusion coefficient
D must be inversely proportional to the radius of diffusing
molecule r, in real cases linear relation between these values
is observed only within homologous or structurally close
solvents and even here with numerous exceptions [3].
Q   H 
OJ ' D  D 
 D 
Q  H  
 D %  D (7  DG   D90 (1)
In this equation D is diffusion coefficient; n is
refractive index and e is permittivity of liquids, that
characterize their polarizability and polarity, which define
their ability to nonspecific solvation; Â is Koppel-Palm
basicity, and Å Ò is Reichardt electrophilicity, that
characterize possible specific (acid-base) interactions; the
square of solubility parameter d2 is proportional to the
cohesion energy of liquids and reflects inputs of energy
for destruction of their structure; Vì is molar volume of
liquids; à³ is regression coefficient.
2. Results and Discussion
Correlation analysis of the obtained equations has
shown that in all cases the molar volume of liquid is
determinative and counteractive as to diffusion; however
acceptable values of multiple correlation coefficient R may
be obtained only by taking into account some other factors.
It is worth noting that in case of aliphatic polymers
nonspecific solvation ability, which is connected with
polarizability f(n2) of liquids, increases the value of D, while
specific solvation ability, which is determined by their
basicity Â, decreases it. Similarly as in cis-isoprene polymer,
dependence of diffusion on solvent properties is also
observed for chloroisoprene polymer. In case of butadiene-
8 Iryna Yevchuk et al.

styrene polymer the influence of medium basicity is reverse.

Therefore it was of interest to examine the influence of wF w F
' 
electronegative but smaller in size fluorine atoms on the wW w[  ,
values of diffusion coefficients. In [6-9] the investigation where ñ is liquid concentration at x distance during t period
results of diffusion of a series of solvents into copolymer of time. The numerical values D were determined from
tetrafluoroethylene-propylene (Aflas FA 100S, 3M Industrial the slope of relations lg (1 – St / S¥ ) vs time t, where S is
Chemical Products Division) are presented. The the quantity of solvent, adsorbed during time t.
investigations were carried out at 303, 318 and 333 K using Corresponding values of D for the investigated liquids are
membranes (14.7´0.225ñm), filled by 30 % carbon black. presented in Table.
Diffusion coefficients were defined based on Fick equation:
Table
Logarithms of diffusion coefficients of the solvents into polymer FA-100S at 303, 318 and 333 K according
to [6-8] and calculated using equations (4-6)
OJ'u
. . .
1R 6ROYHQW
([S &DOF 'OJ'u ([S &DOF 'OJ'u ([S &DOF 'OJ'u
  
 +H[DQH         
 +HSWDQH         
 2FWDQH         
 ,VRRFWDQH         
 1RQDQH         
 'LFKORUR         
PHWKDQH
 GLFKOR         
URHWKDQH
 &KORURIRUP         
 7ULFKORUR    
   
  
HWK\OHQH
 7HWUDFKORUR         
PHWKDQH
 WULFKORUR         
HWKDQH
 7HWUDFKORUR    
   
  
HWK\OHQH
 7HWUDFKRUR         
HWKDQH
 0HWK\ODFHWDWH         
 (WK\O         
DFHWDWH
 0HWK\O         
EHQ]RDWH
 (WK\O         
EHQ]RDWH
 $FHWRQH         
 0HWK\O         
HWK\ONHWRQH
 $FHWRQLWULOH         
 7HWUDK\GUR    
   
  
IXUDQ
 GLR[DQH         
 'LPHWK\O         
DFHWDPLGH
 %XW\ODFHWDWH 
        
 &\FOR 
        
KH[DQRQH
 &\FORKH[DQH 
   
     

* These data are excluded from the calculations
 Regularities of Organic Solvents Diffusion Into Fluoropolymer Structure
Generalization of these data by equation (1) was
made using solvents characteristics from reviews [10,
11]. The calculations were performed in compliance with
recommendations of the IUPAC Group for Correlation
Analysis in Chemistry [12].
Generalization of the data obtained for 26 solvents
at 303 K leads to an equation with unsatisfactorily low
value of multiple correlation coefficient R 0.848; however,
exclusion (according to the recommendations [12]) of
9
D lgD are given. The relation between lgDcal. and lgDexp. is
shown on Fig. 1. As one can see, deviations values, are
normally within the range of mean-root-square error
s = ± 0.160 or exceed it insignificantly (chloroethylene,
tetrachloromethane, ethylacetate, and acetonitrile), but not
more than by ± 2s. More significant deviations are observed
for the three solvents that have been excluded from the
calculations.

OJ'
 FDO
the most deviating data for only three solvents, namely 

cyclohexane, cyclohexanone and butylacetate allows 

obtaining an adequate equation with R > 0.95: 


OJ  ' u      r  I  Q     r  I H  

  r  u   %    r  u  (7 
(2) 


 r  u  G     r  u  90

N = 23, R = 0.965, root-mean-square error s = ± 0.146. 
Maximum value of pair correlation coefficient r was 
observed between lgD and Vì – 0.598 for 26 initial solvents

and 0.729 for 23 solvents used in calculations. Correlation
was not observed with other terms of equation: the          

 OJ'
 H[S
calculated coefficients r are smaller than 0.3, which does
not allow to ascertain their direct influence on lgD.
Significant root-mean-square deviations of
regression coefficient at a number of equation terms,
which often exceed their absolute value, are indicative of
their probable insignificance. That is why, with the goal
to establish a probable effect of individual factors on the
value of D, the successive exclusion of separate terms of
equation each time followed by determining R values for
equations containing smaller number of terms was carried
out. In case when this value decreases insignificantly, the
corresponding excluding term is considered to be
insignificant. Thereby real insignificance of solvation
terms f(n2) and  as well as low significance of ET were
established. Based on the above stated we can conclude
that dependence of D on liquid properties may be described
adequately by three-parameter equation (3):
Fig. 1. Relation between experimental values of lg (D×107)
at 303 K calculated using equation (4)
Similarly, the data obtained at higher temperatures
318 and 333 K were generalized (Table). However in this
case the factor of the electrophilic solvation has to be
additionally considered. This factor increases the value of
D, which is probably due to the fact that values of r
between lgD and Vì are considerably smaller here. Having
generalized 20 available data obtained at 318 K we have
got an expression with R = 0.835; to obtain an acceptable
value of R data for cyclohexane, tetrahydrofuran,
tetrachloroethylene and trichloroethylene need to be
excluded from consideration. Thus, for 16 solvents a six-
parameter equation with R = 0.978 has been obtained, in
which polarizability and basicity terms are insignificant.
OJ  ' u        r   I H  
(3) OJ  ' u      r  I H`  (5)
  r  u   G     r  u   90
 r  u   ( 7 
R = 0.961, s = ± 0.155
and to some extend less adequately by two-parameter  r  u  G   r  u  90
equation (4), which takes into account only the cohesion N = 16, R = 0.978, s = ± 0.094.
energy and the molar volume of the penetrants, whose
penetration into polymer structure gets hindered as it Further excluding of a relatively insignificant term
increases: with f(e) decreases R more significantly – up to 0.926.
OJ ' u       r  u   G   A similar effect is observed for the data obtained at
333 K. The value of R = 0.852 for all 20 solvents after
  r  u  90 (4) excluding from consideration the data for tetrahydrofuran,
R = 0.957, s = ± 0.161. trichloroethylene, and tetrachloroethylene increases to
In Table the values of lgD, calculated using equation 0.975. Factor f(n2) in this case is insignificant; the effect
(4), as well as their deviations from experimental values of basicity is of low significance as well.
10 Iryna Yevchuk et al.

increasing their cohesion and molecules sizes. At the same

OJ  ' u       r   I H  
(6) time insignificance of the solvents basicity B allows to
 r  u  (7  express the opinion about the absence of the assumed
 r   u  G    r  u  90
N = 17, R = 0.953, s = ± 0.111.
In this case further excluding of any term of the
equation from consideration decreases R to undesirably
low values (< 0.95).
Thus, the obtained generalizing equations denote a
common for other polymers mechanism of liquids
diffusion – diffusion decreases with increase of cohesion
and molecules sizes. At the same time insignificance of
solvents basicity factor B allows speculating about the
absence of the assumed donor-acceptor interaction
between fluorine atoms of polymer and electron-donor
carboxylic groups of the solvent, such as carboxylic
groups in esters. The effect of solvents polarity is not
quite clear either. It must be noted that predominantly
polyhalogenderivatives, which have enhanced polarizability,
deviate from general regularities.
In [6-9] the diffusion process activation energies
values ÅD (êJ/mîl) are given. Although the exactness of
their determination by values of D for only three
temperatures seems to be moderate, these values may still
be generalized using the equation of type (1). After
excluding data for cyclohexane, dichloroethane and
chloroform the following equation has been obtained:
donor-acceptor interaction between fluorine atoms of
polymer and electron-donor carboxylic groups of the
solvent, such as carboxylic groups in esters. It should
be noted that predominantly polyhalogenderivatives,
which have enhanced polarizability, deviate from general
regularities.
References
[1] Chalykh A.: Difusiya v polymernyh sistemah. Moskva
1987.
[2] Khinnavar R. and Aminabhavi T.: J. Appl. Polymer. Sci.,
1992, 46, 909.
[3] Aminabhavi T., Harogoppad T., Khinnavar R. et al.: JMS-
Rev., Macromol. Chem. Phys., 1991, C 31, 433.
[4] Makitra R. and Prystansky R.: Zh. Prykl. Khimii, 2004, 77,
1714.
[5] Makitra R., Prystansky R., Zagladko O., Turovsky A. and
Zaikov G.: Russ. Polymer News, 2003, 8, 24.
[6] Aminabhavi T., Harlapur S., Balundgi R. and Ortego J.:
Polymer, 1998, 39, 1067.
[7] Aminabhavi T., Harlapur S., Balundgi R. and Ortego J.: J.
Appl. Polymer. Sci., 1996, 59, 1857.
[8] Aminabhavi T. and Harlapur S.: Chem. Eng. Proc., 1997,
36, 363.
('    r  I  Q   [9] Aminabhavi T., Harlapur S. and Balundgi R.: J. Polymer
 r  I H   Eng., 1997, 16, 181.
(7) [10] Makitra R., Pyrih Y. and Kivelyuk R.: Dep. in VINITI 26. 03.
 r  u  %    r  (7  1986, 628, Â-86.
 r G    r 90
N=17, R = 0.962 s = ± 4.78.
Molar volume Vì has maximum influence on ÅD
value – r between these values equals 0.776. Large standard
deviations at the majority of regression terms indicate their
relative insignificance. Excluding the basicity parameter
decreases R to 0.950, while further exclusion of the terms
with f(n2) and ET makes the correlation invalid.
3. Conclusions
Thus, obtained generalizing equations are
evidences of common with other polymers mechanism
of liquids diffusion, that is decrease of diffusion with
[11] Abboud J. and Notario R.: Pure Appl. Chem., 1999, 71,
645.
[12] Recommendations for Reporting the Results of
Correlation Analysis in Chemistry: Quant. Struct.-Act. Relat.
1985, 4, 29.
ÇÀÊÎÍÎ̲ÐÍÎÑÒ² ÄÈÔÓDz¯ ÎÐÃÀͲ×ÍÈÕ
ÐÎÇ×ÈÍÍÈÊ²Â Ó ÔÒÎÐÂ̲ÑÍÈÕ ÏÎ˲ÌÅÐÀÕ
Àíîòàö³ÿ. Êîåô³ö³ºíòè äèôó糿 îðãàí³÷íèõ ðîç÷èííèê³â
ó ñòðóêòóðó òåòðàôòîðåòèëåí-ïðîï³ëåíîâîãî êîïîë³ìåðà
óçàãàëüíåí³ áàãàòîïàðàìåòðîâèìè ð³âíÿííÿìè. Âèçíà÷àþ÷èìè
¿õ çíà÷åííÿ ³ ñïîâ³ëüíþþ÷èìè ïðîöåñ º ìîëüíèé îá’ºì ³ åíåðã³ÿ
àêòèâàö³¿ ïðîíèêàþ÷èõ ð³äèí.
Êëþ÷îâ³ ñëîâà: áàãàòîïàðàìåòðîâå ð³âíÿííÿ,
êîåô³ö³ºíò äèôó糿, íàáðÿêàííÿ.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 1, 2008
Volodymyr Donchak and Khrystyna Harhay
SYNTHESIS OF FLUORINATED POLYSTYRENE
Lviv Polytechnic National University,
12 Bandera str., 79013 Lviv, Ukraine
donchak@polynet.lviv.ua
Received: October 15, 2007
Abstract. Acylation of polystyrene with trifluoroacetic
anhydride in a solution of aprotonic solvents, namely 1,2-
dichloroethane, chlorobenzene at the presence of Lewis acid
as a catalyst results in obtaining fluorinated polystyrenes,
which possess trifluoroacetic fragments in a benzoic ring,
preferably in the position 4. In order to achieve 70 %
substitution of benzene rings in polystyrene macromolecu-
les, the ratio polystyrene: trifluoroacetic anhydride : AlCl3
must be at least 1:2:4.4 mol correspondingly.
Keywords: modification, polystyrene, trifluoroacetic
anhydride, fluoropolymers
1. Introduction
It is well known, that fluoropolymers are
characterized by a complex of unique properties, such as
high thermal and chemical stability, poor solubility in
organic solvents, biocompatibility etc. [1, 2]. At the same
time another point of a great practical importance is surface
properties of fluoropolymers: poor adhesion, low friction
coefficient, hidrophobicity, high scratch resistance etc [3].
Today fluorinated analogues of all known classes
of polymers are obtained and fluoropolymers are
represented in a wide range. As usual, fluoropolymers are
obtained by the polymerization or polycondensation reaction
of appropriate fluoromonomers [4]. However they are
quite expensive due to complicated production
technologies. This factor is the main barrier on the way to
wide implementation of fluoropolymers.
It was shown by Zisman [5], that perfluorinated
organic compounds are characterized by very low surface
energy. Perhaps the reason of this fact is a well-ordered
construction of the surface layers, which contain –CF2–
or –CF3 fragments. In some specific cases such layers
can form high ordered surface micro hetero phases [6,
7]. Due to their extremely low surface energies polymers
with fluorocarbon segments in side chains have recently
received particular attention [8-19].
On the other hand the surface properties of
fluoropolymers can be reproduced by the method of
introduction of perfluorinated fragments –(CF2)n–CF3 into
traditional polymers.
Chemistry
Today this approach is especially urgent because a
long list of fluorinated organic compounds such as carbon
acids, alcohols, amines etc. are industrial products.
Attaching perfluorinated side chains to traditional polymers
allows combining properties of the last ones with specific
properties of micro hetero phases, formed by
perfluorinated side fragments. This approach was
confirmed by obtaining perfluorinated polyacrylates and
polymethacrylates [20-22].
2. Experimental
2.1. Materials
Polystyrene (PS 148H, Germany), trifluoroacetic
anhydride 99.5 % and AlCl3 (both from Aldrich) were used
without preliminary purification. Solvents (1,2-
dichloroethane, chlorobenzene, dimethylformamide, ether)
were purified in accordance with [23].
2.2. Synthesis of fluoropolystyrene
1.0 g (0,0096 mol) of polystyrene has been loaded
to 150-200 ml three-neck flask, equipped with the stirrer,
condenser, pipe for inert gas purging and thermometer.
The condenser has a small catcher with CaCl2 in his top
part to prevent the water vapour penetration into the
reactor. Polystyrene has been dissolved in 30 ml of dry
1,2-dichlorethane while heating, then cooled to 293 K and
4.0 g (0.0190 mol) of trifluoroacetic anhydride was added
(2 mol per 1 mol of polystyrene). Under the flow of inert
gas 2.53 g (0.0190 mol) of AlCl3 was added by small
batches during 10-15 min and the mixture was stirred
during 1 h at 288–293 K and then 3 h at approx. 353 K.
During this period the mixture becomes yellow and brown.
The suspension is cooled to 293 K, 10 ml of
dimethylformamide (DMFA) is added, then it is filtered
throw the filter paper and the precipitate is washed with
10 ml of 1,2-dichlorethane. 60-70 ml of ether is added to
the filtrate in order to precipitate the modified polystyrene.
After several hours in a refrigerator the liquid is
amalgamated from the resin again. The resin is squashed
with filter paper and dried primarily on air and than under
12 Volodymyr Donchak et al.

vacuum at 333–353 K. Approx 1.5 g of fluorinated 3. Results and Discussion

polystyrene has been yielded as a solid brown substance.
The amount of trifluoroacetic anhydride can be varied
from 1 to 4 mol per 1 mol of polystyrene and the amount
of AlCl3 is 0.5–4.0 mol per 1 mol of trifluoroacetic anhydride.
2.3. Methods of analysis
The content of fluor was determined by the method
described in [24]. Infrared spectra (IR) were obtained using
Specord M-80 apparatus, Carl Zeiss, Jena, Germany, with
the relevant absorption interval in the 4000–400 cm-1 range
and NMR spectra, using Bruker AC-F 300 Ì in CD3–C(O)–
CD3 acetone. Hexamethyldisiloxane was used as the internal
standard. Chemical shift of proton signals was determined
by the positions of centers of symmetry.
&+ &+ 2 &+ &+
&)&
 2
&)&22+
&)&
Polystyrene macromolecules consist of elementary
links of phenyl ethylene, the benzoic rings of which are
activated to electrophilic reagents action due to alkyl
substitute with +²-effect. These rings tend to reactions of
electrophilic substitution and can be slightly acylated under
Friedel-Krafts conditions. This peculiar property of
polystyrene was used for introduction of trifluoroacetic
fragments into benzoic rings. Polystyrene was acylated
by trifluoroacetic anhydride (TFA) in the media of
aprotonic anhydrous solvents (1,2-dichloroethane or
chlorobenzene) in the presence of Lewis acid as a catalyst.
The scheme of the process can be described as follows:
&+ &+

$O&O 
 

2 2 & &)
Q [ \

Q [\

This method allows to adjust the degree of substitution An interpretation of IR spectra of certain fluorinated
and as a result – the content of fluorinated fragments in polystyrenes shows that intensive stretching of carbonyl
modified polystyrenes. The presence of CF3C(O) groups bonds in trifluoroacetic groups – n(Ñ=Î) – appears at
was confirmed by IR and NMR-spectroscopy, element 1664 cm-1, n(їF) stretches – at 1200 and 1152 cm-1.
analysis and by determination of fluorine content. The general The carbon-carbon bonds in a benzoic ring stretch at
characteristics of the products obtained are shown in Table. 1600,1512,1540 cm-1 and d(їÍ) – at 1432, 1368 cm-1.
The amount of ÀlCl3catalyst was equimolar to the TFA amount In 1H-NMR spectrum the protons of acylated rings
in all syntheses. The analysis of NMR spectra shows that appear in downfield at 7.58 (3) and 7.22 (2) ppm.
trifluoroacetic groups enter preferably in n-position in relation Simultaneously, the signals of the protons in unsubstituted
to ethylene substitute. This fact can be explained by the steric rings result at 7.10–7.13 ppm. Aliphatic protons create
hindrances which occur in o-positions. signals in upfield within the range 2.60–1.12 ppm. The
Table shifts of aromatic protons signals in fluorinated
Characteristics of fluorinated polystyrenes polystyrenes to downfield testify the strong electron
accepting properties of trifluoroacetyl fragments.
7KHPRODU &RQWHQWRI 'HJUHHRI The dependence of the degree of substitution (D.S.)
6ROYHQW
UDWLR7)$36W IOXRU VXEVWLWXWLRQ[Q on the molar ratio trifluoroacetic anhydride–polystyrenes
 'LFKORURHWKDQH   is shown in Fig.1.
 &KORUREHQ]HQH   One can see from Fig. 1 that correlation of D.S.
 'LFKORURHWKDQH   with the amount of TFA has the linear character, at the
 'LFKORURHWKDQH  
same time the efficiency of its usage is not high. In order
 'LFKORURHWKDQH  
to achieve the total acylation in the benzene rings, the ratio
of TFA to polystyrene units should be approx. 10 to 1.
Obtained fluorinated polystyrenes contain from 7.3 With regard to the catalyst, its amount affects
to 18.6 % of fluorine, depending on the molar ratio the degree of substitution too. The dependence of the
polystyrene : trifluoroacetic anhydride and insufficiently degree of substitution on the amount of AlCl3 catalyst is
on the nature of the solvent. The acylation occurs a bit shown in Fig.2.
better in 1,2-dichloroethane, due to better solvatation of
intermediate ions. At the same time it can be seen from
Table that no more than 25 % of initial amount of TFA
reacts with polystyrene.
 Synthesis of Fluorinated Polystyrene 13

 

 

 

 

 
' 6 

 
Fig. 1. Dependence of the degree
 
of substitution (D.S.) on the molar ratio
  trifluoroacetic anhydride–polystyrene.
  (Amount of AlCl3 is 1.5 mol per mol of TFA)
 

 
             

P R OH 7 ) $ P R OH 3 6 W














Fig. 2. Dependence of the degree
 of substitution on the molar ratio

catalyst: trifluoroacetic anhydride.
(The ratio PSt:TFA = 1:2)

     
PROH$O&O PROH%7)
TFA

One can see from Fig. 2 that D.S. grows if the amount of the catalyst in the reaction mixture is increased. But
if its amount reaches 2 moles, this increasing becomes inessential.
Such a correlation becomes clear considering the mechanism of the process. Acylation reaction is a typical
electrophilic displacement in the benzoic rings of the polystyrene, in which solvated ion trifluoroacetylium (ÑF3CO+)
or its complex with AlCl3 plays the role of electrophilic agent:
2
&) &
$O&O 2 >$O&O &)&22@>&)&2 $O&O@
&) &
2
In accordance with this scheme the formation of one mole of electrophile (ÑF3CO+) needs 2 mol of AlCl3 per 1
mol of TFA [25]. Furthermore some amount of the catalyst undergoes deactivation due to the interaction with
trifluoroacetic acid, which is the by-product of the acylation reaction:
&)&22+$O&O &)&22$O&O  +&O
The electrophile formed attacks the benzoic ring of polystyrene macromolecule forming at first the s-complex
and then poly(4-trifluoroacetylstyrene):

&+ &+ &+ &+ &+ &+


 &)&2 $O&O  
+
Q $O&O
Q Q
&) & +  & &)
2 $O&O

2
14 Volodymyr Donchak et al.
It is important to highlight that if the degree of
substitution increases the solubility of the polymer in
chlorobenzene and dichloroethane goes down. Fluorinated
polystyrenes with the degree of substitution more than
0.6 are practically insoluble in dichloroethane. They can
be soluble only in dimethylformamide. This fact is very
important if fluorinated polystyrenes would be used for
preparation of polymeric compositions. A poor solubility
in components of composition throws out fluorinated
2
2 2
&)&
2  5)&22+ 5)& 2 & &)
&)&
2
As a result the acylic fragments of other fluorinated
acids could be introduced into polystyrene.
4. Conclusions
1. Trifluoroacetic fragments can be introduced into
the aromatic ring of polystyrene by acylation reaction of
polystyrene with trifluoroacetic anhydride at 353 K in the
media of chlorinated aprotonic solvents.
2. The degree of substitution has a linear correlation
with the ratio trifluoroacetic anhydride : polystyrene.
3. In order to achieve a 70 % substitution of the
benzene ring in polystyrene units the molar ratio
polystyrene : trifluoroacetic anhydride : AlCl3 must be
1:2:4.4 moles correspondently.
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[1] Akemi H., Aoyagi T., Shinohara I., Okano T., Kataoka K.
and Sakurai Y.: Macromol. Chem., 1986, 187, 1627.
[2] Kambic H., Murabayashi S. and Nose Y.: Chem. Eng. News,
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[3] Schmidt D., Coburn C., DeKoven B., Potter G., Meyers G.
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1968, 6, 1729.
polystyrene onto the surface and makes its properties the
same as fluoropolymers have.
Moreover, trifluoroacetic anhydride could be used
as the catalyst for acylation reaction of polystyrene by
another aliphatic fluorinated acid. As a result of the
interaction of trifluoroacetic anhydride with organic acid
the hybrid anhydride is formed, which is able to form
elctrophile from that part of its molecule, which does not
belong to trifluoroacetic fragment [26]:
2 2
  2 & &) 
5)& 
[13] Ramharack R. and Nguyen T.: J. Polym. Sci. C, Polym.
Lett., 1987, 25, 93.
[14] Yokota K. and Hirabayashi T.: Polym. J., 1985, 17, 991.
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[18] Guerry-Rubio C., Viguier M. and Commeyras A.:
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[21] Ameduri B., Bongiovanni R., Malucelli G., Pollicino A.
and Priola A.: J. Polym. Sci. A, 1999, 37, 77.
[22] Corpart J.-M., Girault S. and Juhue D.: Langmuir, 2001,
17, 7237.
[23] Weissberger A. and Proskauer E.: Organic Solvents.
Interscience Publishers, Inc., New York 1955.
[24] Hudlicky M.: Chemistry of Organic Fluorine Compounds.
2nd edn., John Wiley & Sons, 1976.
[25] Norman R. and Taylor R.: Electrophilic Substitution in
Benzenoid Compounds. Elsevier Publishing, New York 1965.
[26] Cope A.: Organic syntheses. An annual publication of
satisfactory methods for the preparation of organic chemicals.
John Wiley & Sons, New York 1950.
ÑÈÍÒÅÇ ÔËÓÎÐÎÍÎÂÀÍÎÃÎ ÏÎ˲ÑÒÈÐÅÍÓ
Àíîòàö³ÿ. Àöèëþâàííÿì ïîë³ñòèðåíó òðèôëóîðîîöòî-
âèì àíã³äðèäîì ó ðîç÷èí³ àïðîòîííèõ ðîç÷èííèê³â (1,2-
äèõëîðåòàíó, õëîðîáåíçåíó) â ïðèñóòíîñò³ êèñëîòè Ëüþ¿ñà ÿê
êàòàë³çàòîðà áóëè îäåðæàí³ ôóîðîíîâàí³ ïîë³ñòèðåíè ç
òðèôëóîðîîöòîâèìè ôðàãìåíòàìè â áåíçîëüíîìó ê³ëüö³,
ïåðåâàæíî â ïîëîæåíí³ 4. Äëÿ äîñÿãíåííÿ 70 % çàì³ùåííÿ â
áåíçåíîâîìó ê³ëüö³ ìàêðîìîëåêóë ïîë³ñòèðåíó íåîáõ³äíî, ùîá
ñï³ââ³äíîøåííÿ ïîë³ñòèðåí:òðèôëóîðîîöòîâèé àíã³äðèä:AlCl3
áóëî â³äïîâ³äíî 1:2:4.4 ìîëü.
Êëþ÷îâ³ ñëîâà: ìîäèô³êàö³ÿ, ïîë³ñòèðåí, òðèôëóî-
ðîîöòîâèé àíã³äðèä, ôëóîðîïîë³ìåðè
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 2, No. 1, 2008 Chemistry

Zoubida Seghier1, 2, Ambroise Diby1, 3, Vanda Voytekunas1, 4,

Philip Cheang5 and Marc J.M. Abadie1, 6

EFFECT OF FILLER TYPE, CONTENT AND SIZE

ON THE UV-CURING DENTAL MATERIALS
1
Laboratory of Polymer Science and Advanced Organic Materials – LEMP/MAO, University
Montpellier 2, Science and Technology of Languedoc, Place Bataillon, 34095 Montpellier Cedex 05,
France, abadie@univ-montp2.fr; marc@ntu.edu.sg
2
University Es-Senia, Oran, Algeria
3
University Cocody of Abidjan, Abidjan, Ivory Cost
4
SIMTech - Singapore Institute of Manufacturing Technology, 71 Nanyang Drive, Singapore 638075
5
School of Chemical & Biomedical Engineering – SCBE, 50 Nanyang Avenue, Nanyang Technological
University, NTU, Singapore 639798
6
School of Materials Science & Engineering – MSE, 50 Nanyang Avenue, Nanyang Technological
University, NTU, Singapore 639798, marc@ntu.edu.sg

Received: December 20, 2007

Abstract. A bis-GMA, TEGDMA monomer mixture at
weight ratio 2:1 was UV-cured with CQ to form commonly
used dental materials. Three types of fillers at different
particle size were added at different weight concentrations.
Reaction rates k, time vs rate were studied for all the
systems.
large quantities are the fumed silicas. A lot of researches
[4-6] were done related to fillers on thermal expansion,
flexural strength and morphology of dental composites.
In this experiment, kinetic aspects of UV-curing of dental
materials based on bis-GMA and TEGDMA with different
types of fillers were studied in detail.

Key words: UV-curing, filler, kinetics, bis-GMA,

TEGDMA.
1. Introduction
A composite is a combination of at least two
chemically different materials (resin and filler) with a
distinctive interface separating the components and having
properties which could not be achieved by any of the
components alone. Filler substances are added to dental
composites for various reasons such as improving the
strength, reducing the shrinkage and reducing thermal
coefficient of expansion, etc.
R. Bowen [1] took the first major step toward dental
composites used nowadays. He strengthened bis-GMA
with ground quartz. The composite was not abrasion
resistant or polish able, and the surface was very rough.
The problem was solved by the introduction of micro
fillers [2, 3]. Filler particles larger than one micron are
classified as macro fillers. Conventional macro fillers were
usually in the range of approximately 30 microns. An
average particle size under 10 microns is found in the
present generation of macro filled composites. Filler
particles under one micron are generally classified as micro
fillers. The only micro fillers commercially available in
2. Experimental
2.1. Materials
· 3 types of fillers are used:
1. SDHA (spray dried HA). It has spherical shape
and was loosely aggregate together with three ranges of
particle: < 25 mm, 45–75 mm, 75–125 mm and density of
3.0 g/ml.
2. RFHA. It has spherical shape and has more dense
structure than SDHA with average particle size at 16 ìm
and density of 3.2 g/ml.
3. ZrO2. It has irregular shape with particle size
less than 1 mm and density of 6.0 g/ml.
The morphology of the three types of fillers is
shown in Fig. 1.
· Dental materials consist of two kinds of monomers
initiated by CQ by UV- curing.
1. Bis-GMA: Bisphenol A-diglycidylmethacrylate,
which is used as monomer.
2. TEGDMA: triethyleneglycol dimethacrylate,
which is used as monomer.
3. CQ: Camphorquinone, which is used as initiator.
Bis-GMA and TEGDMA were used at 2:1 weight
ratio, 3 wt. % CQ was used as initiator for UV-curing.
16 Zoubida Seghier et al.

2.2. Experimental procedure

Kinetic measurements were performed with the
help of the differential photocalorimetry (DPC) technique,
which has been described in the previous papers [7-9]
and allowed to evaluate the heat flow from a photosensitive
formulation that cures when exposed to UV radiation [10]
from the lamp at an intensity of 3mW/cm 2 . The
stoechiometric mixture amounting to about 2.00 mg
monomer mixture and initiator in total was transferred
into the DPC pan. Any oxygen allowed to diffuse into the
sample will scavenge the initiating radicals, retarding the
polymerization. To avoid atmospheric oxygen from
diffusing into the sample, a polyethyleneterephthalate
(MylarÒ film) was used as a cover on top of the liquid
SDHA sample. The DPC pan with the sample was placed into
the DPC cell to equilibrate at a preselected temperature
followed by isothermal treatment without exposure for 1
min, then exposed to UV radiation for 5 minutes. The
exothermic reaction was recorded during the process of
photo curing. The kinetic parameters were calculated using
an autocatalytic model.

3. Results and Discussion

1. Calculate theoretical enthalpy of pure dental resin
with and without fillers.
Since pure dental resin consists of two monomers
(bis-GMA and TEGDMA) in one system, we calculate
their molar ratio as follows:
Bis-GMA has a molecular weight of 512 and
RFHA TEGDMA has a molecular weight of 286, the weight ratio
of the two monomers is 2:1.
Since the enthalpy is defined on the base of the
molar percentage, the 2:1 weight ratio needs to be
converted to molar ratio first.
For bis-GMA: 2g/512=3.9063×10-3 (monomer 1)
For TEGDMA: 1g/286=3.4965×10-3 (monomer 2)
Molar ratio of monomer 1 is equal to 3.9063×10-3/
(3.9063×10-3 +3.4965×10-3), which is 0.528.
Molar ratio of monomer 2 is equal to 3.4965×10-3/
(3.9063×10-3 +3.4965×10-3), which is 0.472.
The enthalpy for the mixture of the two monomers
is defined as:
DHmix = a1[(n1×DH1) /M1] + a2[(n2×DH2) /M2]
where a1 and a2 represent the mole fraction of
monomer 1 and 2 respectively; n1 and n2 represent the
quantity of the double bond in monomer 1 and 2
ZrO2 respectively.
For bis-GMA and TEGDMA, they both have two
Fig. 1. Morphology of different fillers double bonds in the molecular structure. n1 and n2 are
both equal to 2.
 Effect of Filler Type, Content and Size on the UV-Curing Dental Materials 17

DH1 and DH2 represent the heat of polymerization Thus the DHmix of bis-GMA and TEGDMA (2:1 by
(reaction enthalpy) of a single double bond of bis-GMA weight) pure dental material without filler is:
and TEGDMA respectively. These two monomers both DH mix = 0.528×[(2×13.6×4.1868×1000)/512] +
belong to acrylate series, which has a fix DH of 0.472×[(2×13.6×4.1868×1000)/286] = 305.4 J/g
13.6 kcal/mol for a single double bond. Applying When the fillers were added as 10, 20 and 30 wt %,
1 cal = 4.1868 J, DH is 56.94 kJ/mol for acrylate series.
the enthalpy for the filler systems will be 274.8, 244.3
M1 and M2 represent the molecular weight of bis-
and 213.8 J/g respectively.
GMA and TEGDMA, which is 512 and 286 respectively.
Table 1
Experiment results at 303 K
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Note : HA25 means SDHA powder less than 25 mm; HA47 means SDHA powder in the range of 47–75 mm; HA71 means SDHA
powder in the range of 75–125 mm. Based on the individual experiment conducted, SDHA has a maximum loading of 30 wt %. RFHA and
ZrO2 both have a maximum loading of 60 wt %.

2. The results of some kinetic parameters for dental
materials systems with different types and contents of
fillers are listed in Table 1.
The actual enthalpy of the reaction DH is the
indication of heat generated during the polymerization in
an exothermic reaction. The induction time is the time
corresponding to 1 % of the monomer conversion. k is
the reaction constant which, to some degree, indicates
the rate of the reaction. The calculation of the kinetic
parameters is based on the hypothesis that the reaction
may be described by a differential equation:
da(t,T)/dt =k(T)×f(a)
where a is the fraction of the converted monomer,
k(T) the reaction constant depending on the temperature
T and f(a) is a function which represents the hypothetical
model of the mechanism of reaction. In the case of the
kinetic autocatalytic model the approximated differential
equation which is most suitable is:
da(t,T)/dt =k(T)×am×(1-a)n
m and n represent the orders of the priming and
propagation reaction respectively.
The value of n is fixed at 1.5 and that of m is
calculated. From Table 1, it was revealed that all the m
calculated fell in the range of 0.4–0.5. This indicated the
reaction fitted the autocatalytic model very well.
It has an obvious trend for all the systems that
with the increment of the filler, the reaction constant k
increases. That meant the reaction became faster when
the fillers were added in. It could be explained as the result
of fillers’ diffusion of the light emitted by the UV lamp. It
helps the light to penetrate the dental materials during the
curing. This trend could be graphed as in Fig.2 which
represents time vs the reaction rate.
18 Zoubida Seghier et al.

Systems with ZrO2 had higher reaction constant k and lower

WLPHYVUHDFWLRQUDWH induction time t than any other systems with HA powder.
 This could be due to the fact that ZrO2 powder diffused

UV light better than the HA powder because of its smaller
UDWHPLQ


 SXUH size, irregular shape and different chemical structure. It
 +$ was found out that when the fillers had the particle size
 +$ more than 1 mm, i.e. macro fillers, this did not have much
 +$
effect on reaction kinetics such as k when the particle size
 WLPHPLQ
Fig. 2. Reaction rate vs. time of dental material
with fillers at different concentration
It was also obvious that with the increment of filler
content, the reaction rate k increased and in the mean
time the induction time of all reactions decreased, as shown
in Fig. 3. This meant that with the addition of fillers, the
reaction proceeded faster and it took less time to reach
1 % conversion than with the pure dental materials.
.LQHWLFSDUDPHWHUVDWGLIHUHQWILOOHU
FRQFHQWUDWLRQ

5HDFWLRQFRQVWDQW


 changed. When the particle size went down to less than
1 mm, i.e. micro fillers, the influence on reaction kinetics
became very obvious. On the other hand, HA filler presented
a spherical shape whereas ZrO2 filler presented an irregular
one. All the above facts (shape, size, and chemical structure)
could result in better UV light diffusion to the dental material
system during UV-curing.
4. Conclusions
Three types of fillers (SDHA, RFHA and ZrO2) all
accelerated the reaction of bis-GMA and TEGDMA dental
material system. The reaction rate increased with the
increment of content of fillers in the systems. Fillers with

different chemical structure had different reaction acceleration
rate. Out of the studied fillers ZrO2 had the best acceleration
,QGXFWLRQWLPH

effect. Micro fillers had better UV light diffusion rates than
NPLQ





 
  
)LOOHUFRQFHQWUDLRQ
N LQGXFWLRQWLPH
Fig. 3. Effect of filler concentration on the induction time
and reaction constant
Note: data were based on pure dental material and that with filler
of SDHA (10 %, 20 %, 30 %) less than 25 mm.
As for different types of fillers, it was observed that
reaction rate k and induction time t did not differ essentially
for SDHA and RFHA when they were at the same
concentration. It was concluded that particle size of filler,
especially that of macro filler, did not play an important role
in the composites UV-curing kinetics. It was also observed
that there was little difference in k and t when different kind
of HA were added in the system. Both SDHA and RFHA had
a spherical shape and the same chemical structure. The only
difference between these two fillers lied in the micro particles
degree of density. RFHA had a much denser matrix than
SDHA. However, it did not seem to have any influence on
the reaction rate and induction time.
ZrO 2 had a much greater contribution to the
increment of the reaction rate comparing to HA powder.
VHF
macro fillers, which resulted in faster reaction rate.


References

[1] Bowen R.: JADA , 1963, 66, 57.
[2] Mannerberg F.: Quintess. Internat., 1977, 8 (8), 23.
[3] Michl R.: Quintess. Internat., 1978, 9 (3), 29.
[4] Calais J.: J. Dent. Res., 1988, 67, 836.
[5] Li Y. and Swartz M.: J. Dent. Res., 1985, 64, 1396.
[6] Germain H.: J. Dent. Res., 1985, 64, 155.
[7] Abadie M. and Appelt B.: Dent. Mat., 1989, 1, 6.
[8] Appelt B. and Abadie M.: Polym. Eng. Sci., 1988, 28 (6), 367.
[9] Abadie M.: Euro. Coating J., 1988, 5, 350.
[10] Voytekunas V. and Abadie M.: Eur. Chem. Tech. J., 2004, 6, 67.
ÂÏËÈ ÒÈÏÓ, ʲËÜÊÎÑÒ² ² ÐÎÇ̲ÐÓ
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ÑÒÎÌÀÒÎËÎò×Ͳ ÌÀÒÅвÀËÈ
Àíîòàö³ÿ. Ìîíîìåðíó ñóì³ø á³ñ-ÃÌÀ ³ ÒÃÌ-3 ³ç
âàãîâèì ñï³ââ³äíîøåííÿì 2:1 çàòâåðäæóâàëè ÓÔ-
âèïðîì³íþâàííÿì ç êàìôîðîõ³íîíîì äëÿ îäåðæàííÿ
ñòîìàòîëîã³÷íèõ ìàòåð³àë³â çàãàëüíîãî âèêîðèñòàííÿ.
Äîäàâàëèñü òðè ð³çíèõ òèïè íàïîâíþâà÷³â, ç ð³çíèìè ðîçì³ðàìè
÷àñòèí ³ âàãîâèìè êîíöåíòðàö³ÿìè. Äëÿ âñ³õ ñèñòåì âèâ÷àëè
øâèäê³ñòü ðåàêö³¿ òà ¿¿ çàëåæí³ñòü â³ä òðèâàëîñò³ ïðîöåñó.
Êëþ÷îâ³ ñëîâà: ÓÔ-çàòâåðäæåííÿ, íàïîâíþâà÷,
ê³íåòèêà, á³ñ-ÃÌÀ, ÒÃÌ-3.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 1, 2008
Arnold Karateev, Andrew Koryagin, Denis Litvinov, Ludmila Sumtsova
and Yana Taranukha
NEW NETWORK POLYMERS BASED ON FURFURYLGLYCIDYL ETHER
National Technical University “Kharkiv polytechnical institute”
21 Frunze str., 61002 Kharkiv, Ukraine
karateev@kpi.kharkiv.ua
Received: December 26, 2007
Abstract. Among the activities done under the present
work are the following: study of the kinetic regularities
of the polymerization of new heterocyclic monomers
and oligomers obtained from interaction between
furfurylglycidyl ether and aliphatic monocarboxylic acids
(saturated and unsaturated); determination of the
polymerization mechanism in the absence of complex
onium catalysts; determination of the structure and
composition of monomeric and polymeric compounds
by using chemical and physicochemical techniques and
1
Í-NÌR spectral analysis. The kinetic regularities for
polymerization have been studied using differential
scanning calorimetry (DSC); study of the thermal
resistance and thermal stability employed the
derivatography techniques (DTA and TGA).
Keywords: monomer, oligomer, network polymer,
furfurylglycidyl ether, Diels-Alder adducts, complex onium
catalysts.
1. Introduction
The furfurol, furfuryl alcohol and other derivates
of furan are widely employed to obtain synthetic resins
[1]; various furan compounds are used as solvents,
plasticizers, pharmaceutical products, physiologically active
substances, etc.
A wide base for pentosan-containing raw materials,
which are essential for obtaining furfurol and,
consequently, other furan compounds, are determinative
in obtaining synthetic polymer materials based on the furan
derivates, particularly, on furfurylglycidyl ether (FGE) [2].
Of special interest are the reactions forming
network polymers based on the Diels-Alder adducts (DA),
as in this case hyper-branched structures supported by
the polyfunctionality of DA adducts are formed.
The oligomer DA adducts that include halogens (e.g.
chlorine, bromine), form network polymers belonging to
the self-extinguishing polymers group [3, 4].
Chemistry
2. Experimental
FGE was synthesized according the procedure
described in [5], and then vacuum-distilled. The refractive
index is compliant with the published information (1.4810);
the epoxide equivalent is 27.32 %; the main substance content
(MSC) is 98 %. The acrylic acid (AA) was vacuum-frozen,
the acidity index (AI) for the AA is 775.5 mg ÊÎÍ/g.
The MSC is 99.6 %. The linolenic acid (LA) was vacuum-
dried, the iodine number (IN) is 272.4 mg, I2/100g, AI is
198.2 mg ÊÎÍ/g. The MSC is 98 %.
The maleic anhydride was distilled prior to
application, the AI is 1138.5 mg ÊÎÍ/g, which is
compliant with the MSC 99.5 %. Maleimide (Aldrich):
melting point is 364–366 K, MSC is 99 %. 2,4,6-
tribromoaniline (Aldrich): melting point is 393–395 K, the
MSC is 98 %.
Producing 2,4,6-tribromophenylmaleimide, 0.1 mol
of 2,4,6-tribromoaniline and 0.12 mol of maleic anhydride
are suspended in a 70 g of polyphosphoric acid (content
of Ð2Î5 is 72.5 mass %). The suspension is then mixed
thoroughly and heated at 373 K until complete
homogenization. After this step the reaction mass is kept
at 383–393 K for 2 hours and then cooled and mixed with
30 ml of water. The sediment deposit is filtered out, washed
and resolved in isoamyl alcohol; then activated charcoal
is added, and the resulting substance is boiled “with
backflow condenser” for one hour. After boiling, the
product is cooled, filtered and re-deposited in water. The
result is the product of the melting point of 415 K (more
precisely, 415.5 K, according to published data).
The catalysts – complex onium salts of the general
formula given below, have been obtained according the
procedure described in [6, 7].
R4N+×MeHal-x+1, R4P+×MeHal-x+1
where: R4N and R4P+ are the cations of the quaternary
+
ammonium and phosphonium salts, R-ALk, Ar; Me=Zn2+, Fe3+
Furfuryl, hydroxypropylacrylat (FGPA) and
furfuryl, hydroxypropyllinoleat (FGPL) have been
synthesized using the above catalysts at T = 353 K; the
extent of reaction (96 %) was monitored as per the AI.
20 Arnold Karateev et al.

The Diels-Alder adducts have been synthesized at maleimide – 1:1 and 1:2; extent of reaction (90–95 %)
T = 313–333 K, with the molar ratio 1:1, in case of was monitored as per the change of IN (Scheme 1).
QHWZRUNV

NDWWq
NDWWq 2+ 2 NDWWq
2
2 5

2 2 ,,,
2

, 2
5&22+

2 2
2 2
2
,,
2 2 2 1 2
2 2 2
+ 1
+

2 2
2 2
2
2 1 2 2
%U %U

2
%U 2 2

2 2
2
2 2
1 Scheme 1. Heterocyclic polymers and oligomers
,9 2
based on furfurylglycidyl ether
2 2 2
1
%U %U 2+

NDWWq NDWWq
9

%U
QHWZRUNV

The Differential Scanning Calorimetry (DSC) furfurylglycidyl ether (FGE), as samples, in the presence
method was employed to determine the thermal effects of complex onium catalysts specified above. It was
and temperature limits for the course of reactions under determined that a simultaneous polymerization of the
analysis. The reactions were performed in vacuum-sealed double vinyl bonding and the oxirane ring occurred in the
ampoules, the shots weight ranged within 50–100 mg; presence of the above catalysts.
heating rate is 2 K/min. Since the complex onium catalysts are related to
Thermogravimetric research of polymers was the cation catalysts group, the polymerization of
conducted using the “Paulik-Paulik-Erdei” derivatograph. unsaturated glycidyl ethers occurs as a combined
A dry and solidified sample of polymer was analyzed in mechanism in the presence of the above catalysts, i.e. as
the dynamic mode; sample weight was 500 mg, heating a radical polymerization of the double bonding and cation
rate – 5 K/min. polymerization of the oxirane ring.
NMR spectra were recorded on a Varion Mercury To verify the mentioned specific action of complex
VX-200 spectrometer in DMSO-D. onium catalysts, we have polymerized the
Content of the gel-fraction was defined through methylmetacrylate, which rejects polymerization as per
polymer extraction in the Soxhlet apparatus using toluene the cation mechanism [9].
and propanone until their complete weight was reached. As was determined by using DSC technique FGE does
The peroxide and iodine numbers were defined not polymerize in the presence of complex onium catalysts
according to the procedure [8]. Application and testing of of different composition and structure contained in vacuum
coatings was done in compliance with [8]. in sealed ampoules or in a blanket of inert gas. This posed a
question as to the mechanism of FGE polymerization in the
3. Results and Discussion presence of complex onium catalysts in the oxygen
atmosphere, and the role played particularly by the oxygen.
Previously, the authors have studied the kinetics of The furan compounds – furfurol, furfuryl alcohol,
polymerization for unsaturated glycidyl ethers using and others – are known to indicate a high chromophoric
glycidylmetacrylate, vinylglycidyl ether, and effect in the presence of atmospheric oxygen. Being totally
 New Network Polymers Based on Furfurylglycidyl Ether 21

colorless after vacuum distillation, these compounds If we assume that the peroxide compounds occur
acquire a dark-brown tint when contacting with air, and à in the double bondings of the furan ring, this would imply
retinoid state when such contact is long-time, also under a scheme of possible routes for chemical reactions. The
effect of the catalysts [10]. scheme is described below (Scheme 2):

2
2 5&22+
2 OLQROHQLFDFLG

2DLU R&

, ,,

2 2 2
2+ ,,, 2+
2 2 2
5 2 2 2 2 5
2 2

2 2
2 2 2+
2 2 5
2
2

Scheme 2. Routes for chemical reactions in the polymerization mechanism

When studying the kinetics of accumulation of
peroxide groups in the FGE, linolenic (unsaturated) acid
and composition FGE+LA, it was determined that both
the FGE, and the linolenic acid, form – to a slight extent –
peroxide compounds, as shown in Fig. 1; the composition
FGE+LA, upon a certain time period and at 293 K, reaches
the maximum value of peroxide number – 2.31 mmol Î2/g,
and is compliant with reactions 1 and 3 in the presented
reaction route. From the viewpoint of thermodynamics,
route 3 is preferred, since this route retains the most
favorable distribution of electron density for the furan ring,
similar to the formation of DA adducts.

Fig. 1. Kinetics for accumulation of peroxide groups: FGE (1), LA (2), FGE + LA (1:1) (3)
22 Arnold Karateev et al.

The kinetic curves of DSC indicate the contribution (Fig. 2, curve 4), the activation energy decreases, and the
of peroxide compounds at the FGE+LA polymerization. polymerization temperature of double bondings of the furan
When the peroxide of furan ring is of maximum content ring is reduced by 40-50 K (Fig. 2, curves 1 and 4).

323 373 423 473 523 573

Temperature, K

Fig. 2. Thermal effects of interaction between FGE and LA, catalyst – Et3PhCH2N×FeCl4 (1 mass %):
in 7 days (1), in 14 days (2), in 30 days (3), in 45 days (4)

Fig. 3. 1H-NMR spectrum of freshly-distilled FGE

 New Network Polymers Based on Furfurylglycidyl Ether 23

The analysis and interpretation of the 1Í-NÌR fifth carbons, since the initial singlet breakage forms of the
spectrums – FGÅ (freshly-distilled – Fig. 3), and FGÅ fifth and the sixth carbons have changed into the triplet forms,
(kept in the air for two weeks – Fig. 4) also testify to the and the protons of the third and the fourth carbons have
formation of peroxide group between the second and the transferred from the initial singlet form to the multiplet form.

Fig. 4. 1H-NMR spectrum of FGE after keeping in the air for 2 weeks

Fig. 5. 1H-NMR spectrum of monomer I (Scheme 1)

24 Arnold Karateev et al.

Fig. 6. 1Í-NÌR spectrum of monomer II (Scheme 1)

Fig. 7. 1Í-NÌR spectrum of monomer IV (Scheme 1)

 New Network Polymers Based on Furfurylglycidyl Ether 25

The furan [1] and furfuryl alcohol [11] are known
to form the DA (Diels-Alder) [12, 13] adducts with the
maleic anhydride and maleimide.
The paramagnetic spectrography approach for the
1
Í-NÌR has helped determining the structure for the DA
adducts formed: monomer I (Scheme 1, Fig. 5), monomer
II (Scheme 1, Fig. 6).
373 473 573 673 773
Temperature, K
Fig. 8. Dependence of the thermogravimetric analysis of
network polymers: FGPA (1), FGPL (2), monomer II (3),
monomer IV (4). Nontransparent signs are TGA curves,
transparent signs are DTA curves
The area 5.15–5.5 ððì is related to the DA adduct;
the singlet of protons of the third and the fourth carbons
in the initial maleimide within 6.8 ððì of the DA adduct
has split to the multiplet 6.3–6.6 ððì in Fig. 6. The Fig. 7
presents the spectrum of the 1Í-NÌR monomer IV
(Scheme 1).
In the presence of the complex onium catalysts, all
DA adducts form network polymers at the temperature
of 433–453 K.
Derivatography was used to indicate the regions
of thermal stability and thermal resistance for the
network polymers. The loss of 5 % of the weight of a
network polymer occurs at the temperature of 533 K;
thermal decomposition is accompanied by the
exothermic effect reaching its maximum at the
temperature of 633 K. The information for DTA and
TGA is presented in Fig. 8.
Since the resulting heterocyclic monomers and
oligomers are easy-flowing or thick-flowing liquids, they
873
are of considerable interest as chemically resistant
protective coatings with high physico-mechanical indices
as opposed to the known furan resins based on furfurol
and furfuryl alcohol polycondensation products [10, 14].
The properties of coatings based on heterocyclic
monomers and oligomers are presented in Table.

Physico-mechanical properties of coatings

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26 Arnold Karateev et al.
4. Conclusions
1. We have obtained new heterocyclic monomers
and oligomers based on furfurylglycidyl ether, which
provides for considerable increase of the initial range of
substances to be used for paint and composition materials.
2. Under the conditions of polymerizing with the
complex onium catalysts, we have synthesized new
network thermally resistant polymers, which can be used
as chemically resistant protective coatings. New network
polymers feature enhanced physico-mechanical properties
as opposed to the traditional alkyd plastics.
3. We have studied the kinetics and presented the
polymerization mechanism of FGE derivatives.
4. Using the physico-chemical methods and the
methods of 1Í-NÌR spectrography we have determined
the scope and structure of monomers and oligomers.
5. New monomers and oligomers are ecologically
safe, since no organic solvents are involved when using
them as coatings.
References
[1] Gandini A. and Belgacem M.: Prog. Polym. Sci., 1997, 22, 1203.
[2] Karateev A., Koryagin A., Litvinov D. and Sumtsova L.:
3562 Pat. Ukraine, cl. CO1B31/00, CO8L63/04, Publ. 15.11.2004.
[3] Karateev A. et al.: 2028400 Pat. Rus., cl. DO6M11/72,
CO9K21/04, 21/08, Publ. 09.02.1995.
[4] Taranukha Ya. and Karateev A.: Integrovani tehnologii i
energozberezhenija, 2006, 4, 37.
[5] Malinovskiy M. and Golcev V.: Ukr.Khim.Zh., 1967, 9 (33),
920.
[6] Aliev Z., Karateev A. and Atovmian L.: Koordin. Khimia,
1988, 14 (4), 530.
[7] Aliev Z., Karateev A. and Atovmian L.: Koordin. Khimia,
1988, 14 (1), 111.
[8] Gosudarstvennye standarty. Laki i kraski. Izdatelstvo
standartov, Moskva 1974.
[9] Kushch P., Karateev A. and Rosenberg B.: Ukr. Polym.
Zh., 1993, 1 (2), 40.
[10] Choura M., Belgacem M.N. and Gandini A.:
Macromolecules, 1996, 29, 3839.
[11] Jotterand N. and Vogel P.: Tetrahedron Lett., 1999, 40,
5499.
[12] Mcelhanon J., Russick E., Wheller D. et al.: Sandia National
Laboratories, Albuquerque, New Mexico, 87185-88088, 2001.
[13] Gheneim R., Perez-Berumen C. and Gandini A.:
Macromolecules, 2002, 35, 7246.
[14] Litvinov D., Sumtsova L. and Karateev A.: Voprosy Khimii
i Khim. Techn., 2005, 5, 152.
Íβ ѲÒ×ÀÑÒ² ÏÎ˲ÌÅÐÈ ÍÀ ÎÑÍβ
ÔÓÐÔÓÐÈËÃ˲ÖÈÄÍÎÃÎ ÅÒÅÐÓ
Àíîòàö³ÿ. Âèâ÷åíî ê³íåòè÷í³ çàêîíîì³ðíîñò³
ïîë³ìåðèçàö³¿ íîâèõ ãåòåðîöèêë³÷íèõ ìîíîìåð³â ³ îë³ãîìåð³â,
îòðèìàíèõ âçàºìî䳺þ ôóðôóðèëãë³öèäíîãî åòåðó ç
àë³ôàòè÷íèìè ìîíîêàðáîíîâèìè êèñëîòàìè (íàñè÷åíèìè ³
íåíàñè÷åíèìè). Âñòàíîâëåíî ìåõàí³çì ïîë³ìåðèçàö³¿ ó
ïðèñóòíîñò³ êîìïëåêñíèõ îí³ºâèõ êàòàë³çàòîð³â. Áóäîâà ³ ñêëàä
ìîíîìåðíî-îë³ãîìåðíèõ ñïîëóê âñòàíîâëåí³ õ³ì³÷íèìè ³ ô³çèêî-
õ³ì³÷íèìè ìåòîäàìè òà 1Í-ÏÌÐ-ñïåêòðîñêîﳺþ. ʳíåòè÷í³
çàêîíîì³ðíîñò³ ïîë³ìåðèçàö³¿ âèâ÷åí³ ç âèêîðèñòàííÿì
äèôåðåíö³éíî¿ ñêàíóþ÷î¿ êàëîðèìåò𳿠(DSC), òåðìîñò³éê³ñòü
³ òåðìîñòàá³ëüí³ñòü – ìåòîäàìè äåðèâàòîãðàô³¿ (DTA, TGA).
Êëþ÷îâ³ ñëîâà: ìîíîìåð, îë³ãîìåð, ñ³ò÷àñò³ ïîë³ìåðè,
ôóðôóðèëãë³öèäíèé åòåð, àäóêò ijëüñà-Àëüäåðà, êîìïëåêñí³
îí³ºâ³ êàòàë³çàòîðè.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 1, 2008
Witold Brostow and Tea Datashvili
CHEMICAL MODIFICATION AND CHARACTERIZATION
OF BOEHMITE PARTICLES
Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of Materials
Science and Engineering, University of North Texas, Denton, TX 76203 – 5310, USA;
http://www.unt.edu/LAPOM/; brostow@unt.edu, tcd0033@unt.edu
Received: January 10, 2008
Abstract: Polymerizable organic silane molecules
3-(trimethoxysilyl)propylmethacrylate (3MPS) and
vinyltri(2-methoxyethoxy)silane (VTMES) have been
introduced onto surfaces of high purity Boehmite (a
commercial alumina) via hydroxyl groups on the oxides in
order to obtain organic-inorganic hybrid “macromonomers”.
Changes of surface characteristics have been determined
using thermogravimetric analysis (TGA) and Fourier-
transform infrared spectroscopy (FTIR). The influence of
the type of silane used and modification conditions have
been determined. Preheating was applied to some Boehmite
samples; it leads to lower concentrations of –OH groups
on the powder surface and the adsorption yields lower than
in samples without preheating. Modification leads to surface
hydrophobicity and thus reduces significantly water
adsorption; in TGA we see desorption of water below 423 K
only in un-modified Boehmite.
Keywords: Boehmite, macromonomer, silica coupling
agent, surface modification, powder filler.
1. Introduction
We see increasing use of fillers – including those
containing ceramic oxides – in the development of polymer
composites [1]. One thus obtains composites with better
mechanical, thermal, electrical or other properties. This
is particularly important for the ongoing process of gradual
replacement of metallic components by polymer-based
ones. The latter are weak mechanically [2] while ways of
lowering wear are under development [3]. The properties
of polymer-based composites are strongly influenced by
the nature of the filler and also by adhesion between the
filler particles and the polymer [4-16]. In fact, interfacial
tensions are decisive for properties of multiphase materials
[17]. The main problem here is the incompatibility of
hydrophilic ceramic oxide fillers and hydrophobic polymer
matrix which yields composites with poor properties.
Thus, control and/or manipulation of the surface properties
of the particles are of importance. We know that during
the preparation process formation of covalent bonding
Chemistry
between organic polymers and inorganic components
contributes to enhancement of the compatibility in the
composites. This can be achieved through the grafting of
a polymerizable group onto the oxide surfaces via hydroxyl
groups followed by its copolymerization with organic
monomers [18-23]. Among others, silane coupling agents
have been used to improve dispersion, adhesion and
compatibility in such materials [24-28].
The purpose of the present work is modification
and characterization of Boehmite, that is aluminum
oxyhydroxide (AlOOH) powder through adsorption of
polymerizable organic silane molecules 3-(trimethoxysilyl)-
propylmethacrylate (3MPS) and vinyltri
(2-methoxyethoxy)silane (VTMES) onto surfaces of
ceramic oxide powders via hydroxyl groups on the oxides.
In order to obtain organic-inorganic hybrid “macromo-
nomers”, effects of modification conditions have to be
carefully determined to optimize the process.
Additional experiments were conducted on SCA
modified Boehmite powders. These hybrid
macromonomers were blended with low density
polyethylene (LDPE). Investigation of powder loading and
powder morphology effects on thermal, mechanical and
tribological properties of the resulting materials is reported
in another paper [29].
The present paper is one of a series dealing with
polymer + ceramic oxide powder composites. There are
other papers addressing the free radical copolymerization
of the modified SiO2 oxides with methylacrylic monomers
and the characterization of resulting organic-inorganic
hybrids [12, 29, 30].
2. Experimental
2.1. Materials
Silane coupling agents (SCA), namely VTMES – SCA
972 and 3MPS – SCA 989 and high purity Boehmite (under
the HiQ alumina trade name) were received as a gift from
Struktol Company of America and Engelhard Co.,
respectively. Toluene was from Sigma Chemicals Co. All
reagents were of analytical grade and were used as received.
28
2.2. Characterization of Boehmite sample
Boehmite is a low cost material used in many areas;
it is an important precursor because the heat treatment of
Boehmite produces a series of transition aluminas from
g-Al2O3 and h-Al2O3 to d-Al2O3 and q-Al2O3, which exhibit
high surface areas (200–500 m2/g) and thermal stability
up to 1273 K.
Boehmite was thought to exist under two distinct
forms, well-crystallized Boehmite and pseudoboehmite
The chemical composition and physical properties of commercial ceramic powders
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Witold Brostow et al.
(also called gelatinous Boehmite) [31], with significantly
different morphologies, porosity and surface areas.
However, more recent studies [32, 33] have clearly
demonstrated that pseudoboehmite is simply micro- or
rather nano-crystallized Boehmite; the difference observed
between the two forms comes from a difference in
crystallite sizes.
Table 1 lists the chemical composition and physical
properties of the Boehmite commercial ceramic powders.
Table 1
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From Table 1 we see very small sizes of the
crystallites. Generally, the structural elements in Boehmite
crystals consist of double chains of AlO6 octahedra resulting
in double molecules [34]:
2 2.4. Characterization techniques
2+ $O $O2+
2 has been described by Menard and his colleagues [36, 37].
Q Isothermal thermogravimetry (TG) was used to
These chains are parallel, forming layers with the
OH groups outside. The double chains are linked by
hydrogen bonds between hydroxyl ions. Boehmite crystals
exhibit perfect cleavage perpendicular to the general
direction of the hydrogen bonding [35].
2.3. Grafting of SCA onto ceramic
particles
Introduction of reactive groups onto the
commercially obtained and preheated at 3 h 823 K ceramic
surfaces was achieved by a reaction of SCA with the
hydroxyl groups of alumina. Two different types of SCA
were used and the temperature dependence of the process
was characterized.
A typical example can be described as follows.
Reaction mixture contained 25 ml SCA, 200 ml of toluene
and 20 g of powder. After dispersing the powder in solvent
SCA was added and the resulting mixture refluxed at the
boiling temperature of the solution for 24 h. The process
was also conducted with 24 h mixing at room temperature.
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Afterwards the powder was centrifuged and
washed with fresh toluene for 24 h to remove the excess
SCA absorbed on the surfaces. Final products were dried
at 363 K under vacuum for 24 h.
All the samples were analyzed by TGA in nitrogen
atmosphere at the heating rate of 10 K/min. The technique
determine a temperature profile. A Perkin Elmer TGA-7
instrument was used. Several milligrams of each dried
sample were placed on a balance located in the furnace
which was heated over the temperature range from 323
to 973 K.
The FTIR spectra were recorded on a Nexus 470
FTIR ESP Series spectrometer at the resolution of 4 cm-1
wave number, in the midinfrared range from 4000 to
250 cm-1. To enhance the signal to noise ratio, each of the
reference and sample spectra presented constitutes an
average of 40 scans recorded.
For infrared spectroscopy measurements, CsI
pellets containing 1 wt % of material were used and the
background noise was corrected with pure CsI data.
3. Results and Discussion
3.1. Characteristics of the surface
modified Boehmite
The basic principles of the surface modification of
ceramic powder are presented schematically in Figure 1:
 Chemical Modification and Characterization of Boehmite Particles 29

$O 2+  526L $O 2 6L
&+ &+
2

2
&+ &+
$O 2+  52 6L $O 2 6L
2 2
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2
Fig. 1. The surface modification of ceramic powders

Formation of new groups on powder surfaces was diagram in Fig. 3 supports these results, as indicated by the
investigated by Fourier-transform infrared (FTIR) main weight loss between 373 and 773 K.
spectroscopy which is sensitive to both inter- and intra- The reaction that takes place can be simply
molecular interactions. Fig. 2 shows the FTIR spectra of represented by
Boehmite powder before and after modification with two 3AlOOH ® Al2O3 + AlOOH + H2O
polymerizable organic silane molecules, 3MPS and The dehydration of the Boehmite appears to occur
VTMES, onto surfaces of ceramic oxide powders via in three main steps. The first gives a sharp symmetrical
hydroxyl groups on the oxides. endotherm and ends at 423 K. It accounts for 10–13 wt %
of the mass loss. The second step gives a broad unsym-
metrical endotherm and ends before 773 K. It represents
036 the major part of the mass loss, about 15–17 wt %. The
970(6 last step does not correspond to a specific thermal event
but appears as a continuous mass loss. It only corresponds
to about 2–3 wt % of the mass loss.



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Fig. 2. FTIR of Boehmite powder before       
and after modification 7HPSHUDWXUH.
We see that the samples exhibit stretching vibrations Fig. 3. TGA scans of Boehmite powder before
of –OH groups in the 3000–3600 cm-1 range. The vibrations and after heating
appear for unmodified Boehmite powder as strong peaks.
These peaks are characteristic for the –OH fragments of
physisorbed water. A small fraction of these –OH groups The first step has been attributed to the desorption
also appears in modified samples. They are evidence of the of physically adsorbed water, the second step to the
same physisorbed water. Furthermore, we can see a conversion of Boehmite into a-alumina, and the last step
different picture in the case of preheated Boehmite powder to elimination of residual hydroxyls. Several authors [34,
(Fig. 4); namely, these samples do not exhibit stretching 35, 38, 39] explain the asymmetrical profile of the second
peaks in the 3000–3600 cm-1 range due to the desorption peak by removal of chemisorbed water before the
of physisorbed water after heating above 773 K. The TGA convertion into alumina.
30 Witold Brostow et al.

036 



 

 




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Fig. 4. FTIR of preheated Boehmite powder before
and after modification
For modified Boehmite samples small trace peaks
in the region 2800–3000 cm-1 are associated with the
methylene (–CH 2–) and dimethylene (–CH 2–CH 2–)
stretching which comes from polymerizable organic
molecule contamination. We see the same stretching peaks
in the 2800–3000 cm-1 range for polymerizable organic
silane molecules.
Compared with unmodified powder, formation of
peaks is observed in the 800–1700 cm-1 region. These
signals are characteristic for the silane coupling agents.
The characteristic peaks for the modified powders
have the absorption bands at the 1500–1750 cm-1 and
1000–1500 cm-1 range which correspond to unsaturated
bands of the SCA. The strong signal at 1733 cm-1 is
characteristic of the carbonyl (C=O) stretching of the SCA
989 (Fig. 2); the peaks decrease in size for SCA 989 grafted
onto the surfaces of preheated Boehmite powders. This
can be explained by decreasing amounts of –OH groups
on the powder surfaces after heating at 823 K for 3 h
immediately before modification (Fig. 4). As expected,
the mass loss for preheated Boehmite below 823 K is only

3UHKHDWHG%RHKPLWH
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*UDIWHG970(6RQWR3UHKHDWHG%RHKPLWHDW+7
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7HPSHUDWXUH.
Fig 5. TGA scans of Boehmite and preheated Boehmite
powders before and after modification
5.0–7.0 wt % while for the Boehmite powder a
significant mass loss 25.0–27.0 % occurs below 823 K
(Fig. 3).
As noted above, to evaluate organic group reactivity
in the modification process of Boehmite surfaces we have
used SCA 972 and SCA 989 with vinyl and methacryl
groups respectively. The experiments show clearly more
chemical activity of the methacryl groups in SCA 989.
Formation of larger amounts of organic-inorganic hybrid
macromonomers takes place. At the same time SCA 972
provides lower activity and exhibits nearly the same grafting
efficiency for both Boehmite powders. On the other hand,
both SCAs provide higher yields of adsorption onto the
Boehmite particles as compared to preheated samples.
As observed by other authors [26, 40] the main
peak at 1699 cm-1 indicates that SCA 989 monomers are
successfully adsorbed onto the Boehmite and preheated
Boehmite powder surfaces (Figs. 2 and 4) through
covalent bonding. The second system shows weaker
interactions between functional groups of SCA 972 and
 Chemical Modification and Characterization of Boehmite Particles
hydroxyl groups of the preheated powder and even weaker
ones for unheated powder.
A significant difference in thermal behavior between
the unmodified and modified Boehmite samples (Fig. 5)
also indicates the role of the modification efficiency.
At the same time, TGA data reveal hydrophobic
characteristics of the modified powder surfaces; the mass
loss is significant only above 423 K while for unmodified
powders such loss occurs below 423 K due to
physisorbed water desorption. The thermograms of all
the modified samples show two regions of characteristic
weight loss at 423–623 K and 623–823 K. This can be
explained by a decomposition of the organic constituent
of the grafted SCA.
From TGA curves we also see that the modification
process remains the same when reaction temperature ranges
from room to boiling. The use of high temperature treatment
did not cause marked improvement in percentage modification
and adsorption efficiency – as we see in Fig. 5.
Apparently introduction of new groups onto
microsize Boehmite surfaces takes place. A large excess of
the SCA or an increase of the process temperature does
not significantly affect the products since the amounts of
group adsorbed onto the surfaces appears to be limited.
Apparently, growing adsorbed chains of SCA on the powder
surfaces have a blocking effect on the diffusion of monomers
to the surfaces of Boehmite particles.
As already mentioned, mechanical properties of low
density polyethylene (LDPE) reinforced with Boehmite
grafted as described above are reported elsewhere [29].
Finally, we note a large variety of current and potential uses
of Boehmite. To give just one more example, metal catalysts
of hydrogenation reactions in oil refinery industry can be
deposited on porous Boehmite [41].
Acknowledgments
A partial financial support was provided by the Robert
A. Welch Foundation, Houston (Grant B-1203). T. D.
acknowledges also support of the Georgian Research
Development Foundation (GRDF), Tbilisi.
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Àíîòàö³ÿ. Ïîêàçàíî, ùî ïîë³ìåðèçàö³éíîçäàòí³
îðãàí³÷í³ ñèëàíîâ³ ìîëåêóëè 3-(òðèìåòîêñèñèë³ë)
ïðîï³ëìåòàêðèëàòó òà â³í³ëòðè(2-ìåòîêñèåòîêñè)ñèëàíó äëÿ
îäåðæàííÿ îðãàí³÷íî-íåîðãàí³÷íîãî ã³áðèäó “ìàêðîìî-
íîìåð³â” ìîæóòü áóòè ââåäåí³ íà ïîâåðõíþ áåì³ò³â âèñîêî¿
÷èñòîòè (ïðîìèñëîâèé ãëèíîçåì) çà äîïîìîãîþ ã³äðîêñèëüíèõ
ãðóï íà îêñèäè. Çì³íè ó ïîâåðõíåâèõ õàðàêòåðèñòèêàõ âèçíà÷åí³
òåðìîãðàâ³ìåòðè÷íèì àíàë³çîì (ÒÃÀ) òà ³íôðà÷åðâîíîþ
ñïåêòðîñêîﳺþ ç ïåðåòâîðåííÿì Ôóðüº. Âèçíà÷åíî âïëèâ òèïó
ñèëàíó òà óìîâè ïðîöåñó ìîäèô³êóâàííÿ. Âñòàíîâëåíî, ùî ó
ïîïåðåäíüî íàãðiòèõ çðàçêàõ ñïîñòåð³ãàºòüñÿ çìåíøåííÿ
êîíöåíòðàö³¿ –ÎÍ ãðóï íà ïîâåðõí³ ³ çìåíøåííÿ àäñîðáö³éíîãî
âèõîäó ïîð³âíÿíî ³ç çðàçêàìè áåç íàãð³âàííÿ. Ìîäèô³êàö³ÿ
ïðèâîäèòü äî ã³äðîôîáíîñò³ ïîâåðõí³, âíàñë³äîê ÷îãî çíà÷íî
çìåíøóºòüñÿ àäñîðáö³ÿ âîäè; çà ðåçóëüòàòàìè ÒÃÀ äåñîðáö³ÿ
âîäè íèæ÷å 423 Ê ìຠì³ñöå ò³ëüêè â íåìîäèô³êîâàíèõ áåì³òàõ.
Êëþ÷îâ³ ñëîâà: áåì³ò, ìàêðîìîíîìåð, êðåìíåçåìíèé
àãåíò, ìîäèô³êàö³ÿ ïîâåðõí³, ïîðîøêîâèé íàïîâíþâà÷.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 1, 2008
Evgeniy Davydov, Georgiy Pariiskii, Iryna Gaponova,
Tatyana Pokholok and Gennady Zaikov
POLYMERS IN POLLUTED ATMOSPHERE. FREE RADICAL
AND ION-RADICAL CONVERSIONS INITIATED BY NITROGEN OXIDES
Emanuel Institute of Biochemical physics, Russian Academy of Sciences
4 Kosygin str., 119334 Moscow, Russia
pgb@sky.chph.ras.ru
Received: November 22, 2007
Abstract. Nitric oxide, nitrogen dioxide, nitrogen trioxide
as well as dimers of nitrogen dioxide are reactive initiators
of radical transformations of macromolecules and
modifying reactants for polymers. Features of the initiation
mechanism determining the composition of molecular and
radical products in polymers under the action of nitrogen
oxides are discussed.
Keywords: nitrogen oxide, polymer, reaction, radical, EPR
spectrum.
1. Introduction
Nitrogen oxides play an important role in various
chemical processes taking place in an atmosphere and affect
an environment [1-4]. These compounds in increasing
amount are ejected into atmosphere by industrial plants and
motor transport in creating thus a large ecological problem.
Investigations of kinetics and mechanism of reactions
initiated by nitrogen oxides are important for determination
of various organic compounds stability of vegetative and
animal origin as well as synthetic polymeric materials in
conditions of polluted atmosphere. On the other hand,
nitrogen oxides find a wide application for synthetic
chemistry [5-7] and may by used for chemical modification
of polymers, in particular for preparation of spin-labelled
macromolecules [8, 9]. The generation of spin labels takes
place in this case as a consecutive process including
formation and conversion of specific intermediate molecular
products and active free radicals. It is necessary to note
essential advantages of such a way of obtaining spin labels
not requiring application of complex synthetic methods based
on reactions of stable aminoxyl radicals with functional
groups of macroradicals [10]. If the polymers are capable
of reacting with nitrogen oxides, the formation of stable
radicals takes place spontaneously or by thermolysis of
molecular products of nitration [11, 12].
Nitrogen oxides of the three types: NO, NO2, NO3
are the most important for reactions with various organic
compounds and polymers. All of them represent free
Chemistry
radicals with different reactivity [13]. In the present review
the features of the mechanism of these oxides reactions
and also dimers of NO2 with a number of polymers and
low-molecular compounds are considered. The special
attention is given to the analysis of the stable nitrogen-
containing radicals structure and kinetic features of their
formation. On the basis of the results of the analysis, the
conclusions on the mechanism of primary reactions of
initiation and intermediate stages of complex radical
processes under the action of nitrogen oxides are given.
The principles of the nitrogen oxides use for grafting spin
labels upon various polymers are considered.
2. Results and Discussion
2.1. Interaction of nitric oxide with
products of photolysis and radiolysis
of polymers
The NO radical is least reactive among three
examined nitrogen oxides. It is not capable of abstracting
hydrogen atoms even from the least strong tertiary or allyl
C–Í bonds; the strength of H–NO bond amounts is only
205 kJ×mol-1 [14]. Nitric oxide cannot join the isolated double
bonds of the alkenes [15] and initiate radical reactions in
that way. For NO, the recombination with free radicals
with formation of nitroso compounds is a characteristic
process. The structure of stable nitrogen-containing radicals
formed from nitroso compounds (spin traps) in the
subsequent reactions can give information on the mechanism
of radical processes taking place in the reacting system.
Let’s consider such an opportunity by the example
of polymethylmethacrylate (PÌÌÀ). During photolysis
of PÌÌÀ in atmosphere of NO by unfiltered light of a
mercury lamp at 298 K, the formation of
acylalkylaminoxyl radicals R 1 N(O · )C(=O)OR 2 was
observed with typical parameters of anisotropic triplet EPR
spectrum in a solid phase:
$,,1  r  mT J ,, =2.0027 ± 0.0005 [16] (Fig. 1a).
34 Evgeniy Davydov et al.

P7 P7
+ +
Fig. 1. ESR spectra of PÌÌÀ after photolysis (a)
D and radiolysis (b) in atmosphere of NO at 298 K
E

The occurrence of acylalkylaminoxyl radicals is the evidence of eliminating of methoxycarbonyl radicals in the
course of the polymer photolysis:
PMMA KY ~(ÑH )C(COOCH )CH C·(CH )~ (R·) + ·COOCH (1)
o 3 3 2 3 3

The subsequent reaction with participation of NO gives acylalkylaminoxyl radicals:

· 5x ·
COOCH3 + NO ® O=N-COOCH3 o RN(O )COOCH3 (2)

With the help of NO, it was possible to establish JA = 2.0054 ± 0.0005 [16]. As for photolysis,
the nature of intermediate short-lived radicals in a g-irradiation of PMMA is accompanied by the detachment
photochemical process using EPR spectra of stable
nitrogen-containing radicals. of ester groups and the formation of acylalkylaminoxyl
Radiolysis of PMMA in the presence of NO at room radicals similarly to the reaction (1). But radiolysis causes
temperature in addition to acylalkylaminoxyl radicals gives an increase in the contribution of hydrogen abstraction
iminoxyl macroradicals (Fig. 1b) with the following para- from methylene groups of the main chain with the
meters of the ESR spectrum: $ ,,1    r    mT, formation of corresponding macroradicals:
1 J
$A  r  mT ; ,, =2.0025 ± 0.0005,
J ·
PMMA 
o ~(ÑH3)C(COOCH3)C H(CH3)C(COOCH3) ~ (5x) (3)
These macroradicals by recombination with NO are converted into nitroso compounds:
5x + NO ® ~(ÑH3)C(COOCH3)CH(NO)(CH3)C(COOCH3)~( 5xNO) (4)
Nitroso compounds having a-hydrogen atom are easily transformed into oximes which in reaction with active
methoxycarbonyl radicals form registered stable iminoxyl radicals:
x
&22&+
5x NO ® ~(ÑH3)C(COOCH3)C(=NOH)(CH3)C(COOCH3)~   
o
·
~(ÑH3)C(COOCH3)C(=NO )(CH3)C(COOCH3)~ + HCOOCH3 (5)

Thus the composition of stable nitrogen-containing
radicals reflects primary reactions taking place in PMMA
under the action of light and g-radiation.
The application of nitric oxide enables to prepare
spin-labelled macromolecules in chemically inert and
insoluble polymers, for example in polyperfluoroalkanes.
As was shown in the work [16], the radiolysis of
polytetrafluoroethylene (PTFE) oriented films and
copolymer of tetrafluoroethylene with hexafluo-
ropropylene initiates reactions with the formation of
iminoxyl macroradical according to the following
scheme:

J J J
PÒFE o ~ ÑF2C·FCF2 ~ + NO ® ~ 
 o ÑF2CF(NO)CF2 ~ 
o
· ·
~ ÑF2C (NO)CF2 ~ ® ~ ÑF2C(=NO )CF2 ~ (6)
J 12 J
~ ÑF2CF(CF3 )CF2 ~ o ~ ÑF2CF(CF2 NO)CF2 ~ 
o
· ·
~ ÑF2CF(C FNO)CF2 ~ ®~ ÑF2CF(CF=NO )CF2 ~ (7)

Aminoxyl radicals in polyperfluoroalkanes are not macroradicals appear with conversion into fluoroaminoxyl
·
formed under these conditions. However, if one carries macroradicals ~ ÑF2CF(NO )CF2 ~ by the subsequent
out g-irradiation in the air, middle and end peroxide exposure to NO. Their ESR spectra in oriented films are
 Polymers in Polluted Atmosphere. Free Radical and Ion-Radical Conversions Initiated by Nitrogen Oxides 35

quintet of triplets (Fig. 2) with the parameters: The NO 3 radicals are characterized by high
reactivity in reactions with various organic compounds
$,,1 =0.46 mÒ, $,,) =1.11 mÒ, J ,, =2.006; [18-22]. Typical reactions of these radicals are abstraction
of hydrogen atoms from C–H and addition to double
$A1 =1.12 mÒ, $A) =1.61 mÒ and J A =2.0071. bonds. Furthermore, nitrogen trioxide can appear as an
oxidizer of organic compounds. Along with these reactions,
the radicals NO 3 are decomposed in thermal and
photochemical processes. The thermal decomposition of
nitrogen trioxide generated by pulse radiolysis of
concentrated water solutions of a nitric acid takes place
with high rate (k208Ê = 8×10 3, s –1) [23]:
N7
NO3 o
 NO2 + Î (18)
P7 The radicals NO3 have three intensive absorption
+ bands in visible region of an optical spectrum with l max =
Fig. 2. ESR spectrum of PFTE films previously 600, 640, 675 nm, and in UV region at 340–360 nm [18,
g-irradiated on air after subsequent exposure to NO 19, 23-27]. Under the action of light, NO3 dissociates by
two mechanisms including formation of NO2 and atomic
The following mechanism of the aminoxyl radical oxygen similarly to reaction (18) or nitrogen oxide and
formation in these conditions is proposed [17]: molecular oxygen [1]:
· ·
~ ÑF2 ÑF2 C F CF2 ~ ® ~ C F2 + CF2=CFCF2~ (8) NO3 ® NO + O2 (19)
The end alkyl radical is oxidized into the end The efficiency of the NO3 conversion by one or
peroxide radical: either mechanisms is determined by spectral composition
· ·
~ C F2 + Î2 ® ~ CF2ÎÎ (9) of light. Above 570 nm, NO3 decomposes into NO and Î2
In NO atmosphere, the end peroxide radicals are with the very high (~ 1) quantum yield; the basic products
converted as follows: of the photolysis are NO2 + O below 570 nm. One of the
· · most widespread ways of NO3 generation is the photolysis
~ ÑF2CF2ÎÎ + NO ® ~ ÑF2CF2Î + NÎ2 (10) of Ñå (IV) nitrates in particular ceric ammonium nitrate
· (CAN) (NH4)2Ce(NO3)6. The absorption spectrum of CAN
~ ÑF2CF2Î + NO~ l ÑF2CF2ÎNO (11)
· · has a wide and intensive band with the maximum at
~ ÑF2CF2Î ® ~ Ñ F2 + COF2 (12) 305 nm (e = 5890 l × mol–1×ñm–1) which is conditioned by
· an electron transfer to Ñå4+from nitrate anion. Under the
~ Ñ F2 + NO ® ~ ÑF2NO (13)
12 action of light in the given spectral region there is a
~ ÑF2NO + CF2=CFCF2~ 
o photoreduction of CAN [26, 27]:
·
~CF2N(O )CF2CF(NO)CF2~ (14) KQ
Ñå4+ 12  o
 Ce3+ + NO3 (20)
Thus, spin-labelled macromolecules of fluoroalkyl
polymers can be prepared by using postradiating free Thus, the CAN photolysis gives different active
radical reactions in NO atmosphere. radical particles: NO, NO2, NO3 and atomic oxygen.
Application of light of various spectral composition allows
2.2. Radical reactions initiated to generate these particles in different ratio. Atomic oxygen
by nitrogen trioxide being a very active reactant [14] interacts with C–Í bonds
of organic compounds. Macroradicals formed by the
The radicals NO3 play a significant role in chemical action of atoms O on polymers can be converted in the
processes occurring in the top layers of atmosphere [18]. presence of NO into stable aminoxyl radicals. The use of
These radicals are formed in reaction of nitrogen dioxide
these processes for the purposes of chemical modification
with ozone:
of polymers is considered by the example of
NO2 + O3 ® NO3 + O2 (15)
Under the action of daylight, nitrogen trioxide is polyvinylpyrrolidone (PVP) in the work [28].
consumed with liberation of atomic oxygen: The formation of NO2 by reactions (20) and (18)
KQ in the process of CAN photolysis is confirmed by ESR
NO3 o  NO2 + O (16)
spectra obtained at 77 K. The spectrum at the initial stage
Its disappearance occurs in reaction with nitrogen
of irradiation of PVP with CAN (0.05–0.2 mol×kg –1) by
dioxide at night:
NO3 + NO2 ® N2O5 (17) light with l > 280 nm is shown in Fig. 3a.
36 Evgeniy Davydov et al.

P7
 P 7
E +

Fig. 3. ESR spectra PVP with CAN irradiated by light Fig. 4. ESR spectra of PVP with CAN irradiated
with l > 280 nm at 77 K during 2 min (a) and 60 min (b) by light with l > 280 nm at 295 K

It represents basically a triplet signal with obviously J [[ 2.0066, J \\ 1.9929, J ]] 2.0024.

expressed anisotropy of g-factor and hyperfine structure. During the further irradiation, additional lines appeared on
Essentially, it is in accordance with a spectrum of NO2 a background of the NO2 signal, which belongs most likely
radicals trapped in ice at 77 K [29]. The analysis of to radicals of PVP (Fig. 1b) formed as a result of the
Fig. 3a has given much the same values of A and g-tensors: following reaction:
À õõ = 3.31 mT, À óó = 4.93 mT, À zz = 5.31 mT, and

a&+&+&+a 2

a&+&&+a
1 1 2+ (21)
2 2

5

The radicals R 1 are stabilized only at low $,,1 = 2.0024 (Fig. 4). The cross-linkage of PVP
temperatures (77 Ê). Photolysis of samples at 298 K by macromolecules takes place under these conditions with
the same light results in the production of stable the formation of a gel-fraction as a result of the
dialkylaminoxyl radicals characterized by anisotropic ESR recombination of macroradicals R1 with nitric oxide:
triplet spectrum with parameters of J ,, = 3.18 mÒ and

2
1
12 5
5 a&+&12&+a a&+&&+a

1 12
 (22)
2
a&+&&+a

1
P 

  2
 
J



D
>5@ PRONJ

 
<LHOGRIJHOIUDFWLRQP

 
 
 
E
 
Fig. 5. Yields of gel-fraction and aminoxyl radicals during photolysis of PVP
   
with CAN in concentrations of 0.19 mol×kg - 1 (a) and 0.13 mol×kg - 1 (b)
  
W  V by light with l > 280 nm at 295 K
 Polymers in Polluted Atmosphere. Free Radical and Ion-Radical Conversions Initiated by Nitrogen Oxides
Both processes of gel and aminoxyl radical
formation are in direct correlation during photolysis of
PVP with CAN. The linear dependencies shown in Fig. 5a
and b indicate that fact. Formally, the kinetics of any
product N formation with monotonously decreasing rate
can be represented by the equation:
N = atn (23)
where a and n are empirical parameters, and
0 < n < 1. One can see from Fig. 5a and b, kinetic curves
are linearized in the same co-ordinates of equation (23).
The value of parameter n = 0.88 is obtained from analysis
of kinetic dependencies by a least-squares method. Such
regularity confirms the mechanism (22), according to
which the aminoxyl radicals are formed with participation
of nitric oxide and can be considered as crosslinks for
macromolecules. If crosslinking were to occur in some
other way, for example, by direct recombination of radicals
37
R1, aminoxyl radicals and gel accumulations would not be
correlated as follows from Fig. 5a and b. Such a simple
method of crosslinking PVP can be applied for obtaining
hydrogels used as specific sorbents [30].
2.3. Free radical and ion-radical reactions
under the action of nitrogen dioxide and
its dimers
Nitrogen dioxide effectively reacts with various low-
and high-molecular organic compounds [5-7, 31]. However,
it must be emphasized that NO2 is a free radical of moderate
reactivity, and the ONO–H bond strength [14] makes up
320 kJ mol–1. Therefore, radicals NO2 are capable of
initiating free radical reactions by abstraction of hydrogen
atoms from the least strong, for example, allyl C–Í bonds
or addition to double Ñ=Ñ bonds [32, 33]:

& & 12  & & 12 

This process causes further radical conversions of olefins with formation of dinitro compounds and nitro
nitrites:
21 & & 12 
& & 12 12
212 & & 12 

From Jellinek’s data [31], butyl rubber destroys under the action of NO2:

a&&+ &+a 12 a&&+&+12 a
As a consequence of primary reactions of nitrogen
dioxide radicals with the isolated double bonds, stable
aminoxyl radicals can be generated. Such transformations
are characteristic for rubbers.
2.3.1. Preparation of spin- labelled rubbers
The possibility of obtaining spin-labelled rubbers
by interaction of their solutions in the inert solvents with
the mixture of nitrogen dioxide and oxygen has been
demonstrated in the work [34]. Such rubbers can be
prepared simply and rapidly by reactions of block
polymeric samples with gaseous NO 2 [35]. The
experiments were carried out on 1,4-cis-polyisoprene (PI)
and copolymer of ethylene, propylene and dicyclo-
pentadiene. The samples had the form of cylinders of 1.5
cm height and 0.4 cm in diameter. On exposure of these
polymers to NO2 (10-5–2.3×10-3 mol×l-1) at 295 K, identical
ESR spectra were registered. The spectra represent an
anisotropic triplet with parameters which are typical for
dialkylaminoxyl radicals with $,,1 = 3.1 mÒ and J ,, =
=2.0028 ± 0.0005 (Fig. 6a). The spectra
GHVWUXFWLRQ 
with such parameters testify that the correlation time of
rotational mobility tñ at the given temperature exceeds
10 –9 s. At increasing temperature up to 373 K, the isotropic
triplet signal with J = 1.53 ± 0.03 mÒ and = 2.0057 ±
±0.0005 was observed (Fig. 6b), that is caused by essential
decreasing correlation time (5×10-11 < tñ < 10-9 s). The
change of tñ with temperature (Fig. 7) is described by the
relation tñ = t0exp(E/RT), where logt0 = -14.2, and Å is the
activation energy of rotational diffusion (34.7 kJ×mol–1 ).
The scheme of the aminoxyl radical formation
includes three basic stages: generation of macroradicals
in reaction of NO 2 with rubbers; synthesis of
macromolecular nitroso compounds and spin trapping of
macroradicals by nitroso compounds.
As can be seen from this scheme, the accumulation
of aminoxyl radicals should be accompanied by cross-
linkage of macromolecules. The presence of oxygen
inhibits the aminoxyl accumulation as a result of
conversions of primary nitroalkyl and allyl macroradicals
into peroxide radicals.
38 Evgeniy Davydov et al.

&+
a&+&&+ &+a +12

&+ &+
a&+& &+&+a12 a&+&&+&+a
1
2 2

&+ &+
a&+&&+&+a a&+& &+&+a &+
1 2+ a&+&&+&+a
 2 12
2
a&+&&+ &+a
&+

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

ORJ W  F V


E
D



P7 P7
+ +  
 
Fig. 6. ESR spectra of PI after exposure to NO2 at 295 K (a)
and 373 K (b)
2.4. Mechanism of initiation of radical
reactions by nitrogen dioxide dimers
As noted above, nitrogen dioxide can initiate free
radical reactions in compounds containing weakest C–Í
bonds or double Ñ=Ñ bonds. However, the effective
formation of stable nitrogen-containing radicals was also
observed in aromatic polyamidoimides, polycaproamide,
polyvinylpyrrolidone (PVP) [8] and also aromatic
polyamide (ÀP) [12]. These facts allow considering other
 7.
Fig. 7. Temperature dependence of the correlation time
of rotational diffusion of PI macromolecules measured
using aminoxyl radicals as spin labels
probable mechanisms of the radical processes initiation.
The fact is that the basic radical products of interaction
of nitrogen dioxide with polymers containing amide groups
are iminoxyl and acylalkylaminoxyl radicals which are
produced from oximes and acylnitroso compounds [8,
12]. The occurrence of these predecessors of stable
radicals is in turn connected with the nitric oxide formation.
In this connection, a participation of NO2 dimeric
forms in radical initiation should be considered. The main
dimers of NO2 are planar nitrogen tetroxide O2N–NO2 (PD)
 Polymers in Polluted Atmosphere. Free Radical and Ion-Radical Conversions Initiated by Nitrogen Oxides 39

and nitrosyl nitrate ONONO2 (NN). Ab initio calculations play the role of an intermediate compound at oxidation of
[33] show that these dimers are formed with the most nitric oxide by oxygen [36]. As NN has strong oxidative
probability in NO 2 atmosphere; the form of nitrosyl properties [37], the generation of radicals can take place
peroxynitrite ONOONO is too unstable to be considered by an electron transfer from donor functional groups with
as an efficient participant of reactions, however it can the formation of intermediate radical cations [9, 38]:
- -
RH + ONONO2 ® [R·H+(NO×××ONO2 )] ® R· + NO + H+ + ONO2 (29)
The recombination of radicals with nitric oxide certain obstacles connected with energetic properties of
forms nitroso compounds that undergo isomerisation into NO2 dimers [33] for realizing such mechanism; the energy
oximes [39] to produce iminoxyl radicals in the reaction of syn- and anti forms of NN exceeds that of PD
with NO2: respectively 29.8 and 18.4 êJ×mol-1; that is the equilibrium
·
>C=NOH + NO2 ® >C=NO + HNO3 (30) 2112 12 21212 (32)
The tertiary nitroso compounds are effective spin should be shifted to PD in a gas phase.
traps and the source of stable aminoxyl radicals:
· The diamagnetic PD is capable of generating
R1N=O + R2 ® R1(R2)N-O· (31) nitrogen-containing radicals in a specific reaction with the
Thus the mechanism involving reactions (29-31) system of the conjugated double bonds of p – quinones
could formally explain an appearance of stable radicals in (Q) [40]. On exposure of Q to nitrogen dioxide, the
the polymers not containing specific chemical bonds formation of radicals of oxyaminoxyl type (Roxy) [41] takes
reacting with NO2 mono radicals. However, there are place by the following scheme:
2 2
+ +
12  2 112   2 12  
21
+ +
2 2
5 R[\
The triplet ESR spectrum of radicals Roxy in Q (Fig. calculated from known equilibrium constants are shown
8) has parameters: AN = 2.82 mT and g = 2.0053. in Fig. 9, from which it is clear that the experimental
The mechanism (33) is confirmed by kinetic data. values of the initial rates depend linearly on the partial
The relationships between the initial rates of the Roxy pressures of N2O4 and not of NO2. Thus, both forms of
accumulation and partial pressures of NO2 and N2O4 NO2 dimers can be active.
31 2 3D

 

   










:

P7
   
+
312  3D



Fig. 8. ESR spectrum of Roxy obtained by the exposure Fig. 9. Dependence of initial rates of accumulation
of Q to nitrogen dioxide at 295 K of Roxy at 295 K on partial pressures of NO2 and N2O4
40 Evgeniy Davydov et al.
2.5. Experimental confirmations
of ion-radical mechanism of polymers
nitrosation
Registration of radical cations by the ESR method
in the presence of nitrogen dioxide could provide direct
experimental evidence that the initiation proceeds via NN
by scheme (29). However, because of high reactivity and
fast decomposition [42], these particles are difficult to
detect by this method. Nevertheless, the formation of
radical cations can be revealed indirectly in the act of
their decomposition with detachment of a proton. The
possibility of detecting radical cations during their
decomposition accompanied by the proton emission has
been demonstrated by the example of interaction of
nitrogen dioxide with poly(2-vinylpyridine) (PVPyr).
Pyridine is known to be capable of accepting protons to
yield pyridinium cations. Hence, if protons are formed
during decomposition of radical cations by reaction (29),
they can be detected easily from IR spectra typical to
&+ &+&+  12212  &+ &+&+ 
1 1
12 212 
&+ &+&+  +212  &+  &+&+ 
pyridinium cations. Note that pyridine conversions can
be nitrated only under quite severe conditions. For
example, N-nitropyridinium nitrate was obtained only when
pyridine was treated with NO2 – ozone mixture in an inert
solvent [43]. However, nitrogen dioxide efficiently
interacts with PVPyr.
Fig. 10 represents the IR spectra of the original
PVPyr films and the same films exposed to NO 2
(5×10-4 mol×l-1) [38]. After 90 min exposure at room tem-
perature, two intense bands were observed in the spectrum
at 2400–2600 and 2200 cm-1 corresponding to the stret-
ching vibrations of NH+ pyridinium cations [44]. The bands
at 1600–1430 cm-1, attributed to the stretching vibrations
of C=C and C=N bonds of pyridine rings, are present in the
initial spectrum of PVPyr [44]. During exposure to NO2, a
band at 1650 cm-1 corresponding to the stretching vibrations
of C=N+ bonds arises in the spectrum simultaneously with
the bands at 2400–2600 and 2200 cm-1. This process may
be schematically depicted as follows [38]:
&+ &&+  +12212 
1

1 212  
1+

Thus pyridine rings fix an occurrence of radical cations
as a result of an electron transfer to NN, and in doing so the
ion-radical mechanism (29) is experimentally confirmed. It
is possible to believe that such oxidative mechanism of
generating radicals is characteristic for compounds with the
ionization potential providing electron transfer from donor
groups of molecules to NN. This regularity can be followed
from examples of thermal and photochemical nitration of
7



aromatic compounds under the action of nitrogen dioxide.
According to UV spectroscopy data, NN can form charge-
transfer complexes with methylbenzenes [45, 46]. For the
complexes, a bathochromic shift in the corresponding
absorption bands was observed with an increase in number
of methyl substituents in the benzene ring. This shift correlates
with a decrease in the ionization potential from 8.44 to
7.85 eV passing from p-xylene to hexamethylbenzene.






      

Fig. 10. IR spectra of the original PVPyr films (1)

Q and after exposure to NO2 (2)
 Polymers in Polluted Atmosphere. Free Radical and Ion-Radical Conversions Initiated by Nitrogen Oxides 41

2.6. Effect of nitrogen dioxide on aliphatic
and aromatic polyamides
Oxidative ion-radical mechanism of conversions
induced by NN explains high activity of aliphatic
polyamides and AP to nitrogen dioxide as well as the nature
of stable radicals and molecular products of nitration.
Amide groups can serve as donor electrons in polyamides.
The regularities of aliphatic transformations in particular
polycaproamide [8, 9] may be described by the following
scheme:


&+&21+&+ 21212 &+&21+&+
12212

&+&21&+ +12212

12
&+&21&+ 12 &+&21&+ 
212 2
&+&21&+ 12 &+&21&+ &+&21&+ 12

Reactions (35) at durable exposure lead to
practically full disappearance of -NH- groups in macromo-
lecules. Amidyl macroradicals leaving the “cage” are
decomposed with breaking the main chain and can also
be converted into N-nitrite by recombination with the
monomer form of NO2. The decomposition of N-nitrites
is registered in polycaproamide acylalkylaminoxyl
macroradicals. The ESR spectrum of these radicals is
shown in Fig. 11. It represents a triplet anisotropic signal
1
with $,, = 1.94 mT and J ,, = 2.003. In IR spectra of
polycaproamide exposed to nitrogen dioxide, stretch bands
of N=O in nitroso amide groups at 1504 and 1387 cm-1
are also observed (Fig. 12).

'


E
P7 
+




    


QFP
Fig. 11. ESR spectrum of polycaproamide Fig. 12. IR spectra of original films of polycaproamide (a)
after exposure to NO2 at 295 K and after exposure to NO2 (b)

The main free-radical products of AP (poly-m- corresponds to a spectrum of iminoxyl radicals (I) in a
phenylene isophthalamide) exposure to NO2 are iminoxyl solid phase. At later stages (Fig. 13 b), a signal of the
radicals of two isomeric forms [12]. At the initial stage of second iminoxyl radical (II) appears. The spectrum of
the AP exposure, the ESR spectrum shown in Fig. 13a is radicals II is also anisotropic triplet but with other
observed. It represents anisotropic triplet with parameters: $ 1= (4.1 ± 0.1) mT, J = (2.0024 ± 0.0003)
1 __ __
$ 1= (4.8 ± 0.1) mT, $A = (2.0024 ± 0.0003) and 1
and $ = (2.6 ± 0.1) mÒ, J A = (2.0050 ± 0.0003).
__ J J = (2.0047 ±0.0003). By A
__ = (3.2 ± 0.1) mT, A Based on the mechanisms (29, 30), the process of iminoxyl
its specific form and measured parameters, this signal radical formation is represented schematically as follows:
42 Evgeniy Davydov et al.

2 2 2 2
21212 
& +1 1+& & +1 1&

12212

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

12+212

2 2 2
2
& 1+ 1& & 1+ 1&
+ +
12 12

12 12
2 2 2
2
& +1 1& & +1 1&
2 1
+12
, ,,
Thus, the interaction of AP with NO2 by the ion-
radical mechanism is capable of initiating conversions of
chemically inert phenyl rings into much more reactive
cyclohexadiene groups.
2.7. Conversion of nitrogen dioxide PD
into NN under the influence of amide
groups of macromolecules
As indicated above, the equilibrium (32) should be
shifted to PD in a gas phase due to the higher energy of
NN in comparison with that for PD [33]. Nevertheless,
the effective formation of stable radicals is observed in
polyamides exposed to nitrogen dioxide by ion-radical
mechanism. On this basis it is possible to suggest that the
shift of equilibrium (32) to the formation of NN in
polyamides is caused by specific donor-acceptor
interaction of PD with amide groups which induce the

1
2 +12
conversion into NN and consequently the ion-radical
process by the scheme (29). As the indicator of PD
conversion into NN, the dependence of the yield of
oxyaminoxyl radicals (Rîxy) and iminoxyl radicals (Rim)
on the contents of ÀP (poly-m-phenylene isophthalamide)
in the composites of AP with p-benzoquinone (Q) has
been used. As noted above, the formation of Rîxy and Rim
is connected correspondingly with PD and NN. The results
obtained are shown in Fig. 14. One can see from the figure,
the concentration of radicals R oxy accumulated
monotonously decreases with the increase of ÀP relative
content, while concentrations of Rim radicals vary within
10–20 % of the average value, that is, within the accuracy
of integration of ESR spectra. This fact indicates obvious
dependence of the Roxy yield on the contents of polymers
with amide groups in composites, suggesting that PD is
converted under the influence of amide groups into NN
 Polymers in Polluted Atmosphere. Free Radical and Ion-Radical Conversions Initiated by Nitrogen Oxides 43









P7
  

+ 
$3 4

Fig. 13. ESR spectrum of AP after exposure Fig. 14. Dependence of concentrations of Roxy (1)
to NO2 at 295K and Rim (2) in Q + ÀP after exposure to NO2
on weight ratio of Q and ÀP

that generates stable radicals Rim in AP. It is significant
that an appreciable decrease of the yield of Roxy radicals
was not observed in control experiments when polymers
of other chemical structure, for example, acetyl cellulose
were used in composites with Q. Therefore one can
conclude that amide groups play special role in the
PD ® NN process.
The decrease of a relative yield of Roxy radicals
while adding polymers with amide groups to composites
(Fig. 14) is apparent from the formal kinetic scheme:

4N
5R[\
N
12 3' 
N DN N
>3'D@ >11D@ 5LP
N

where a is an amide group. Taking into
consideration the stationary state of PD, NN, [PD×××a],
[NN×××a] concentrations, the following equations for rates
of accumulation of radicals Roxy and Rim can be obtained:
Thus the rate of accumulation of Rim radicals is
determined by > 12  @ , and concentrations of these radi-
cals accumulated on exposure to nitrogen dioxide do not
depend appreciably on AP contents (Fig. 14, curve 2). In
G > ,@ NN  >4@N    N  > 12  @
(38) contrast, the yield of Roxy decreases as the polyamide is
GW N    N N   N >4@  N>D @  N  N>D @ added to composites and [a] is increased. These diagram
points are representative of competitive pathways for PD
G >,, ,,,@ NNN >D @> 12  @ interactions with Q and amide groups.
GW N  N N   N >4@  N>D @  N N>D @ (39)
where > 12  @ is the concentration of nitrogen dioxide in
a gas phase, [a] is the concentration of amide groups.
These equations can be simplified if concentrations of
amide groups in composites are comparatively high, and
the conversion of PD into NN occurs rather effectively,
that is N  >D @ !! N   N  . Then
2.8. Ab initio calculations
of energies for conversions
of nitrogen dioxide dimmers
For validating the mechanism proposed of the
conversion of PD into NN, the calculations of energy
changes in the process of nitrogen dioxide interaction with
the simplest amide (formamide) have been carried out
within the framework of density functional theory by the
G >5 [\ @ NN  N    N > 12  @ Gaussian 98 program [47]. The B3LYP restricted method
(40)
GW N N  > D @ for closed and open shells was used. The aim of the
calculations is to correlate energy consumptions for
G > 5 LQ @ PD ® NN with those for other stages of the radical
N (41)
GW generation process. The energies of the following states
according to scheme (37) were calculated:
44 Evgeniy Davydov et al.

2NO2 + NH2COH (42) formed in the subsequent reactions are converted into stable
O2N-NO2 + NH2COH (43) radicals. By this way, spin labels can be inserted even to
ONONO2 + NH2COH (44) chemically inert polyperfluoroalkanes. However, the
[O2N-NO2××× NH2COH] (45) chemical structure of macromolecules can be essentially
changed in that case of rather hard conditions of radical
[ONONO2××× NH2COH] (46)
· generation. In this connection, nitrogen trioxide obtained
N HCOH + NO + HNO3 (47) by photolysis of the Ñå (IV) nitrates is promising in
·
NH2CO + NO + HNO3 (48) application for spin labels synthesis. Under the action of
The geometry optimization of all structures was visible and close UV light on these additives, the radicals
performed applying the basis set 6-31G (d, p). The given and nitric oxide are formed simultaneously with
process includes intermediate molecular complexes of PD transformation finally into spin labels. The light of such
and NN with formamide (45, 46). The changes of minimum spectral composition does not cause undesirable side
energies are shown in Fig. 15. One can see the formation effects on macromolecules. Nitrogen dioxide is capable
of PD from NO2 is energetically advantageous process [33], of interacting with the least strong C–Í and double C=C
whereas NN is generated from NO2 in an endothermic bonds initiating thus radical reactions in the given system.
reaction. The complexation of PD with formamide is The dimeric forms of nitrogen dioxide actively react by
accompanied by the release of energy: mechanism depending on the chemical structure of those
DÅ = 28 kJ×mol-1. However, PD in the complex (45) is not forms. The dimers in the form of nitrosyl nitrate represent
capable of reacting with formamide and can leave only the oxidizing agent initiating ion-radical reactions with the
reacting cage. At the same time, PD in the complex can be formation of stable nitrogen-containing radicals. Amide
converted approximately with the same energy consumption groups can induce a transition of energetically less
into NN (46), which further reacts by the electron transfer capacious planar dimers of NO2 into nitrosyl nitrate. This
reactions (47, 48) giving radicals, nitric oxide, nitric acid specific ion-radical mechanism determines the high activity
and significant release of energy (44–57 kJ×mol-1). Such relative to NO2 even with such stable polymers as aromatic
sequence of transformations seems to be more efficient in polyamides.
comparison with a direct interaction of NN and formamide
by state (44), as the energy of dimers in complexes (45)
and (46) is lower than that of an initial state (42). References
[1] Graham R. and Johnston H.: J. Phys. Chem., 1978, 82, 254.
(KDUWUHHV [2] Johnston H. and Graham R.: Canad. J. Chem., 1974, 52, 1415.
 [3] Stroud C., Madronich S., Atlas E., Ridley B., Flocke F. et

al.: Atmospheric Environment, 2003, 37, 3351.
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[5] Titov A.: Tetrahedron, 1963, 19, 557.
 [6] Topchiev A.: Nitrovanie uglevodorodov i drugih organicheskih
soedinenij. Acad. of Sci. of the USSR, Moskva 1956.
  [7] Novikov S., Shveyhgeymer G., Sevastyanova V.and

Shlyapochnikov V.: [in:] Khimiya aliphaticheskih
  alicyclicheskih nitrosoedinenij. Khimiya, Moskva 1974.
 [8] Pariiskii G., Gaponova I. and Davydov E.: Russ. Chem.
 Rev., 2000, 69, 985.
[9] Pariiskii G., Gaponova I., Davydov E. and Pokholok T.:

 [in:] Zaikov G., Buchachenko A., Ivanov V. (eds.), Aging of
polymers, polymer blends and polymer composites. Nova
Fig. 15. Changes of minimum energies calculated Science Publishers, New York 2002.
for reactions of NO2 with formamide [10] Vasserman A. and Kovarsky A.: Spin labels and spin probes
in physical chemistry of polymers. Nauka, Moskva 1986.
[11] Gaponova I., Davydov E., Pariiskii G. and Pustoshny V.:
3. Conclusions Vysokomol. Soed. (A), 2001, 43, 98.
[12] Pokholok T., Gaponova I., Davydov E. and Pariiskii G.,
Nitrogen oxides are the effective initiators of radical Polym. Degrad. Stability, 2006, 91, 2423.
reactions for a number of polymers with formation of [13] Bonner F. and Stedman G.: [in:] Feelish M. and Stamler J.
various molecular nitration products and stable nitrogen- (eds.), Methods in nitric oxide research. Wiley, Chichester 1996.
containing radicals. Nitric oxide does not react directly, [14] Ranby B. and Rabek J.: Photodegradation, photo-
but it recombines with free radicals formed in polymers oxidation and photostabilization of polymers. Wiley, London
by UV photolysis or g-radiolysis. The nitroso compounds 1975.
 Polymers in Polluted Atmosphere. Free Radical and Ion-Radical Conversions Initiated by Nitrogen Oxides
[15] Park J. and Walton J.: J. Chem. Soc., Perkin Trans. 2, 1997,
2579.
[16] Gaponova I., Pariiskii G. and Toptygin D.: Vysokomolek.
Soed., 1988, 30, 262.
[17] Gaponova I., Pariiskii G. and Toptygin D.: Khimich. Fizika,
1997, 16, 49.
[18] Neta P. and Huie R.: J. Phys. Chem., 1986, 90, 4644.
[19] Vencatachalapathy B. and Ramamurthy R.: J. Photochem.
Photobiology A: Chem., 1996, 93, 1.
[20] Japar S. and Niki H.: J. Phys. Chem., 1975, 79, 1629.
[21] Atkinson R., Plum C., Carter W., Winer A. and Pitts J.:
J. Phys. Chem., 88, 1210.
[22] Itho O., Akiho S. and Iino M.: J. Org. Chem., 1989, 54, 2436.
[23] Pikaev A., Sibirskaya G., Shyrshov E., Glazunov P. and
Spicyn V.: Dokl. Akad. Nauk SSSR, 1974, 215, 645.
[24] Hayon E. and Saito E.: J. Chem Phys., 1965, 43, 4314.
[25] Dagliotti L. and Hayon E.: J. Phys. Chem., 1967, 71, 3802.
[26] Glass P. and Martin T.: J. Am. Chem. Soc., 92, 5084.
[27] Wine P., Mauldin R. and Thorn R.: J. Phys. Chem., 1988,
92, 1156.
[28] Davydov E., Afanas’eva E., Gaponova I. and Pariiskii G.:
Org. Biomol. Chem., 2004, 2, 1339.
[29] Atkins P., Keen N. and Symons M.: J. Chem. Soc., 1962,
2873.
[30] Naghash H., Massah A. and Erfan A.: Eur. Polym. J.,
2002, 38, 147.
[31] Jellinek H.: Ch. 9 [in:] Aspects of degradation and
stabilization of polymers. Elsevier, New York 1978.
[32] Giamalva D., Kenion G. and Pryor W.: J. Am. Chem. Soc.,
1987, 109, 7059.
[33] Golding P., Powell J. and Ridd J.: J. Chem. Soc., Perkin
Trans. 2, 1996, 813.
[34] Gyor M., Rockenbauer A. and Tudos F.: Tetrahedron
Lett., 1986, 27, 4795.
[35] Pokholok T. and Pariiskii G.: Vysokomolek. Soed. (A),
1977, 39, 1152.
45
[36] McKee M.: J. Am. Chem. Soc., 1995, 117, 1629.
[37] White E.: ibid., 1955, 77, 6008.
[38] Davydov E., Gaponova I., Pariiskii G. and Pokholok T.:
Polym. Sci. (A), 2006, 48, 375.
[39] Feuer H.: The chemistry of the nitro and nitroso groups,
Wiley, New York 1969.
[40] Davydov E., Gaponova I. and Pariiskii G.: J. Chem. Soc.,
Perkin Trans. 2, 2002, 1359.
[41] Gabr I. and Symons M.: J. Chem. Soc., Faraday Trans.,
1996, 92, 1767.
[42] Greatorex D. and Kemp J.: J. Chem. Soc., Faraday Trans.,
1972, 68, 121.
[43] Suzuki H., Iwaya M. and Mori T.: Tetrahedron Lett., 1997,
38, 5647.
[44] Bellamy L.: The infra-red spectra of complex molecules.
Methuen, London 1957.
[45] Bosch E. and Kochi J.: J. Org. Chem., 1994, 59, 3314.
[46] Bockman T., Karpinski Z., Sankararaman S. and Kochi J.:
J. Am. Chem. Soc., 1992, 114, 1970.
[47] Frisch M., Trucks G., Schlegel H., Scuseria J. et al.:
Gaussian 98, Gaussian Inc., Pitsburgh, PA 1998.
ÏÎ˲ÌÅÐÈ Â ÇÀÁÐÓÄÍÅÍ²É ÀÒÌÎÑÔÅв.
²ËÜÍÎ-ÐÀÄÈÊÀËÜͲ ÒÀ ÉÎÍÍÎ-ÐÀÄÈÊÀËÜͲ
ÏÅÐÅÒÂÎÐÅÍÍß, ÂÈÊËÈÊÀͲ ÎÊÑÈÄÀÌÈ ÀÇÎÒÓ
Àíîòàö³ÿ. Îêñèäè, ä³îêñèäè òà òðèîêñèäè àçîòó
ðàçîì ç ä³ìåðàìè ä³îêñèäó àçîòó º ðåàêö³éíîçäàòíèìè
³í³ö³àòîðàìè ðàäèêàëüíèõ ïåðåòâîðåíü ìàêðîìîëåêóë ³
ìîäèô³êóþ÷èìè ðåàãåíòàìè ïîë³ìåð³â. Ðîçãëÿíóò³ îñíîâí³
ñòà䳿 ìåõàí³çìó ³í³ö³þâàííÿ, ÿêèé âèçíà÷ຠñêëàä
ìîëåêóëÿðíèõ ³ ðàäèêàëüíèõ ïðîäóêò³â â ïîë³ìåðàõ, âèêëèêàíå
îêñèäàìè àçîòó.
Êëþ÷îâ³ ñëîâà: îêñèä àçîòó, ïîë³ìåð, ðåàêö³ÿ, ðàäèêàë,
EÏÐ-ñïåêòð.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 1, 2008
Oleg Grynyshyn, Michael Bratychak, Volodymyr Krynytskiy and Volodymyr Donchak
PETROLEUM RESINS FOR BITUMENS MODIFICATION
Lviv Polytechnic National University
12 Bandera str., 79013 Lviv, Ukraine
mbratych@polynet.lviv.ua
Received: January 11, 2008
Abstract. The process of tar and industrial petroleum resin
“Piroplast-2” joint oxidation has been investigated. The
experimental results of the main regularities researches of
the obtaining process of petroleum resins with carboxyl
groups based on the pyrocondensate C 9 fraction of
hydrocarbon feedstock pyrolysis have been shown. It has
been established that synthesized petroleum resins may
be used for the modification of petroleum bitumens.
Keywords: tar, blown bitumen, petroleum resin, carboxyl
group, modification, bituminous -polymeric composition.
1. Introduction
Petroleum resins obtained via oxidation, deep vacuum
distillation or other methods sometimes do not meet
demands for the marketable products [1, 2]. Bitumen
produced today in Ukraine has low adhesive activity due to
the peculiarities of its obtaining, as well as to the properties
of initial raw material. This fact results in the bitumen film
intensive lift-off from the surface of solid materials under
the action of temperature difference, water, mechanical load
etc. Moreover, bitumen can not be produced using any
kind of feedstock. Therefore, different additives able to
improve bitumen properties are used for the production of
blown and residual bitumens [3-6]. Energy saving
(temperature decrease, reduction of oxidation time) is also
the main direction of process improvement.
Petroleum resins (PRs) are among additives which may
be used for the modification of petroleum bitumens. Such
oligomeric products are obtained via oligomerization of
unsaturated compounds presented in the liquid products of oil
stock pyrolysis. The C5 and C9 fractions of pyrocondensate or
pyrolysis heavy resin are used for the PRs production.
The Department of Chemistry and Technology of
Petroleum at Lviv Polytechnic National University has
carried out a raw of investigations concerning the
modification of blown bitumens produced by Ukrainian
refineries by different petroleum resins.
The bitumens were modified using two methods:
– PRs introdiuction into feedstock for the oxidation
process;
– PRs introduction into finished bitumen.
Chemical Technology
2. Experimental
The joint oxidation of oil tar and petroleum resins
was carried out at laboratory-scale plant consisting of reactor
block, air supply and cooling systems, as well as trapping
unit for oxidation volatile products. A tar, extracted from
Russian export oil mixture was taken at JSC “Ukrtatnafta”,
Kremenchuk with the following characteristics: viscosity
23.2 s, flash point 525 K, softening temperature 303 K,
d420 = 0.991. “Piroplast-2” industrial petroleum resin with
softening temperature 358 K was obtained via thermal
oligomerization of the pyrocondensate C9 fraction of
gasoline pyrolysis. Ductility, penetration and softening
temperature were determined for blown petroleum bitumens
by standard procedures [7].
The C 9 fraction obtained at the pyrolysis of
hydrocarbon feedstock at JSC “Lukor, Kalush, was used
as the raw material for the production of petroleum resins
with carboxyl groups (PRCs). The characteristic of initial
material is presented in [8]. Peroxide with carboxyl end
groups was the initiator of cooligomerization process. Its
formula is given below.
&+ 2 2 &+
+& & 22 & & 22 & &+
&+ &+
+2 & & 2+
2 2
Di-tert-butyldiperpyromellitate (PPM)
PRCs were synthesized in glass ampoules by volume
of 5×10-5 m3. The ampoules were blown with inert gas and
the sample of the C9 fraction was loaded. Then the initiator
was added, the ampoules were soldered and loaded into a
thermostat. After the experiment the ampoules were cooled
and the contents were precipitated with petroleum ether.
The solvent was separated, the obtained residue was dried
at 323 K under vacuum and the product was analyzed.
We investigated 3 commercial oil bitumens
produced by Ukrainian refineries, namely:
48 Oleg Grynyshyn et al.

Table 1
Characteristics of commercial blown bitumens
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BN-70/30 bitumen, produced at JSC “Galychyna”,
Drogobych;
BNK-45/190, produced at Shebelinka Gas-Works;
BN-60/90, produced at JSC “Ukrtatnafta”,
Kremenchuk.
The main characteristics of the mentioned bitumens
are presented in Table 1.Five different types of industrial
and synthesized petroleum resins were used as modifiers:
Pyroplast-2 PR – solid, light-yellow, industrial
product obtained via thermal oligomerization of the C9
fraction. The softening temperature is 358 K.
Dark PR was obtained via thermal oligomerization
of pyrolysis heavy resin. It is a dark-brown substance
with the softening temperature 378 K.
Light PR was obtained via thermal oligomerization
of the C5 and C9 fraction of pyrolysis pyrocondensate. It
is a light-yellow substance with the softening temperature
355 K.
PR with epoxy groups was obtained at the
Department of Chemistry and Technology of Petroleum
at Lviv Polytechnic National University. It is light-brown
substance with softening temperature 355 K. Its
characteristics: molecular mass (M n) is 850, epoxy
number (e.n.) is 8.2 %, bromine number (b.n.) is 9.3 g
Br/100 g.
PR with carboxyl groups was obtained at the same
Department. It is a light-brown substance with the
softening temperature 358 K. Its characteristics: Mn is
1320, e.n. is 8.2 %, b.n. is 9.3 g Br/100 g.
Bitumen-polymeric compositions were prepared by
mixing the components on the laboratory-scale plant
consisting of electrical heater, metal reservoir equipped
with stirrer and thermometer. Samples were weighted,
loaded into the reservoir and heated to 383 K with constant
stirring. Then the calculated amount of PR was added.
The components were stirred until the mixture became
homogeneous at 393 K (the temperature has to be higher
than PR softening temperature).
 ± 
  
  
  
± DEVHQFH ±
±  ±
±  ±
±  ±
3. Results and Discussion
3.1. Joint oxidation of heavy residues and PR
In order to study joint oxidation the main regularities
of heavy residues and PR it was necessary to determine
the PR optimum content in the feedstock for obtaining
blown oil bitumens and to find out how the main
processing factors influence the oxidation rate and thus
characteristics of obtained bitumens.
The effect of Pyroplast-2 content in the feedstock
(tar) on the properties of blown bitumens was studied
with the aim of determination of PR optimum content.
So, PR was introduced into the feedstock in amount of
1–10 mass %. The oxidation was carried out at 523 K for
3 h. The volumetric flow rate was 2.5 min-1. The obtained
results are presented in Table 2.
One can see from Table 2 that introduction of
Pyroplast-2 resin into the feedstock essentially affects the
properties of obtained oil bitumens. The increase of PR
amount increases bitumen softening temperature and ductility
but decreases penetration which determines bitumen
hardness. At the same time the increase of PR content in the
feedstock increases acid number of modified bitumens. This
fact has a positive effect on the adhesive properties which
are characterized by the index “adhesion to glass”. Thus, the
introduction of PR into the feedstock essentially affects the
characteristics of obtained bitumens and increases their
adhesion to the solid surfaces. The mixture with the tar:PR
ratio equal to 95:5 was used for the further investigations.
In order to establish the process optimum
temperature we examined the effect of oxidation
temperature on the properties of obtained oil bitumens.
The investigations were carried out in two parallel
directions: joint oxidation of tar and PR with the ratio 95:5
and tar oxidation without PR. The oxidation process was
carried out for 3 hrs within the temperature range of 483–
543 K. The volumetric flow rate was 2.5 min-1. The
obtained results are presented in Table 3.
 Petroleum Resins for Bitumens Modification 49

Table 2
Effect of PR amount in the feedstock on the properties of blown oil bitumens
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Table 3
The effect of oxidation temperature on the properties of oil bitumens
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Table 4
The effect of oxidation time on the properties of blown oil bitumens
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At joint oxidation of tar and 5 % of petroleum resin
main the characteristics of obtained bitumen are changed
with the temperature increase. We can see from the
experiments that the softening temperature increases
smoothly. At the same time ductility has an extreme
character. This value increases till 523 K and then
decreases. Bitumen penetration decreases with the
temperature increase. At tar oxidation without modifier
(see Table 3) the bitumen characteristics are changed in a
lesser degree. Evidently, that tar oxidation with PR and
without modifier proceeds in a different way. Tar oxidation
without PR proceeds with lower rate. So PR affects the
oxidation mechanism and reduces the process duration.
Further investigations were carried out at 523 K as an
optimum temperature.
The effect of the process time was examined during
3–9 hrs at 523 K and air flow rate 2.5 min-1. The obtained
results are presented in Table 4.
As we can see from Table 4, oxidation time
essentially affects the properties of obtained bitumens.
With the increase of oxidation time the bitumen softening
temperature increases and the penetration decreases. The
dependence of ductility upon oxidation time has an extreme
character, the same as in the previous case.
50 Oleg Grynyshyn et al.

The comparison of bitumens obtained by different
ways shows that PR introduction into the feedstock allows
to achieve definite operational characteristics in a shorter
period of time, that, in its turn, intensifies the process and
saves energy supply. So, PRs may be used as modifiers
of oil bitumens.
3.2. Obtaining of petroleum resins with
carboxyl groups
Since there is a direct dependence between acid
number of modified bitumens and their ability to hold on
the surface (index “adhesion to glass”) it should be necessary
to synthesize petroleum resins with carboxyl groups (PRC)
and to investigate them as modifiers of bitumens. To our
mind, the introduction of oligomers with carboxyl groups
will exactly improve the adhesion properties of oil bitumens.
PRC obtaining was studied via initiated
coologomerization of unsaturated hydrocarbons presented
in the C9 fraction in the presence of PPM functional
peroxide. The experiments were carried out in the
temperature range of 393–413 K and PPM amount
0.25–5.0 mass %. The process time was 5–50 h.
Functional oligomers with different characteristics
(Tables 5 and 6) were obtained under different conditions
(temperature, initiator amount, process time). The main
characteristics are: molecular mass, bromine number
which corresponds to the resin unsaturation and acid
number which characterizes the carboxyl group content
in the cooligomer molecule.
We can see from Table 5 that the increase of the
initiator amount increases the PRC yield and acid number
but decreases its molecular mass. Obviously, it is the result
of molecules formation with less size but greater amount
of carboxyl groups. The increase of functionality (f)
reveals the same fact. The increase of the initiator amount
decreases PRC bromine number.
The increase of oligomerization temperature (see
Table 5) increases PRC yield, decreases molecular mass
and increases acid number, it results in the increase of
PRC functionality. The unsaturation of PRC is reduced
because we observe the decrease of bromine number.
The results from Table 6 show that the increase of
synthesis time increases PRC yield, molecular mass and
bromine number but decreases acid number and PRC
functionality.
Obtained results allow to offer the optimum
conditions for PRC obtaining: temperature 393 K, time –
50 h, PPM content – 2.5 mass %, calculated on the
feedstock. Synthesized PRC is a solid, light-brown
substance, which is soluble in aromatic solvents, dioxane,
carbon tetrachloride etc. Its characteristics are: yield is
20.2 mass %, M n = 1320, br.n. = 23.8 gBr 2 /100g,
a.n. = 51.9 mg KOH/100g, functionality is 1.22.

Table 5
The effect of initiator amount on the PRC yield and main characteristics

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 Petroleum Resins for Bitumens Modification 51

Table 6
The effect of cooligomerization time on the PRC yield and main characteristics
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3.3. Modification of oil bitumens
by petroleum resins
Synthesized petroleum resins with carboxyl groups
were used for the modification of oil bitumens. The
modification of blown oil bitumens was carried out via
PRC introduction into BN-70/30 industrial bitumen
produced at JSC “NPK-Galychyna”.
The PRC amount ranged from 1 to 10 mass %.
Four other types of PR were introduced in the same
bitumen in the same amount for the comparison. The
results are presented in Table 7. As we can see from the
experiments the introduction of petroleum resins increases
bitumen softening temperature. Moreover such increase
is correlated with PR softening temperature; it means
bitumen-polymeric composition containing dark petroleum
resin has the maximum softening temperature.
The investigated bitumen has the minimum ductili-
ty – 3 cm. The introduction of PR does not change the
ductility. The increase of PR amount increases the bitumen
hardness (index “penetration”). Bitumen with 10 mass %
of dark PR has the minimum penetration (1 mm).
The ability to hold on the surfaces (adhesion ability)
is one of the main characteristics of building bitumens.
This ability is characterized by the index “adhesion to
glass”. One can see from Table 7 that in all cases
introduction of PR increases the adhesion. Moreover, the
greater PR amounts, the greater index “adhesion to glass”.
The presence of functional groups in the investigated PRs
has a stronger influence on the bitumen adhesion. The
best results are obtained using PR with carboxyl groups.
For instance, the introduction of 10 mass % of such
oligomer increases the adhesion from 81.9 to 99.6 %,
that is also correlated with acid number of bitumen-
polymeric composition. This fact confirms the hypothesis
about the improvement of adhesion properties by carboxyl
groups.
Other bitumen-polymeric compositions on the bases
of BNK-45/190 and BN-60/90 commercial bitumens
(produced at Shebelinka Gas-Works and JSC “Ukrtatnafta,
correspondingly) were obtained and analyzed for the
comparison. The results are presented in Tables 8 and 9.
BNK-45/190 bitumen is very similar by its
characteristics to BN-70/30 bitumen produced at JSC
“NPK-Galychyna”. That is why obtained values
characterizing the effect of different types of PRs on the
bitumen properties are also similar to the mentioned values.
One can see from Table 8 that the increase of PR amount
in the bitumen-polymeric composition increases its
softening temperature and decreases penetration. The
composition ductility actually is not changed. Like in the
previous case, the increase of PR amount improves the
adhesion characteristics of the bitumen-polymeric
compositions, which result in the increase of the “adhesion
to glass” index. The best results have been obtained using
PR with carboxyl groups.
BN-60/90 bitumen produced at JSC “Ukrtatnafta”
(see Table 9) has the same regularities except ductility. In
contrast to the previous cases the introduction of PR
increases the ductility but at the PR amounts more than
5-7 mass % the ductility is reduced.
52 Oleg Grynyshyn et al.

Table 7
The effect of PR amount on the characteristics of BN-70/30 produced at JSC “NPK-Galychyna”
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The effect of PR amount on the characteristics of BNK-45/190 bitumen produced at Shebelinka Gas-Works”
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 Petroleum Resins for Bitumens Modification 53

Table 9
The effect of PR amount on the characteristics of BN-60/90 bitumen produced at JSC “Ukrtatnafta”
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4. Conclusions “Nauchno-tehnicheskie problemy dorognoi otrasli stran

On the basis of above-mentioned results we may
assert that petroleum resins may be used as active additives
of bitumen-polymeric compositions. Their introduction
to the bitumen structure has a positive effect on the
operational characteristics, especially on the adhesion
properties. The optimum amount is 5 mass % but this
value may be changed depending upon the expected result.
References
[1] Gun R.: Neftyanye bitumy. Khimiya, Moskva 1973.
[2] Grudnikov I.: Proizvodstvo neftyanyh bitumov. Khimiya,
Moskva 1983.
[3] Kuzora I., Gogotov A., Moiseev V. and Pyhtin V.: Sposob
poluchenia polymer-bitumnoi kompozicii ipolimera-
modifikatora. A.c., Publ. 20.07.2002.
[4] Strahova N., Pavlyukovskaya O. and Berdnikov V.: Tezisy
dokladov konferencii “Problemy dobychi i pererabotki nefti i
gaza v perspective megdunarodnogo sotrudnichestva
uchenyh Kaspijskogo regiona”, Astrahan’, 2000, 103.
[5] Vyrogemskiy V., Kirichenko L. and Kyshchynskiy S.:
Sbornik tezisov I nauchno-prakticheskoi konferencii
SNG”, Ìîskwa, 2000, 176.
[6] Vakhrusheva E., Ryabov V. and Artemov V.: Tezisy
dokladov 29 nauchnoi konferencii “Khimiya I khimicheskaya
technologia”, Perm’, 1998, 57.
[7] Nefteprodukty. Masla, smazki, prysadki. Izdatelstvo
standartov, Moskwa 1987.
[8] Dumskiy Yu., No B. and Butov G.: Khimiya i technologiya
neftepolymernykh smol. Khimiya, Moskwa 1999.
ÂÈÊÎÐÈÑÒÀÍÍß ÍÀÔÒÎÏÎ˲ÌÅÐÍÈÕ ÑÌÎË
ÄËß ÌÎÄÈÔ²ÊÀÖ²¯ Á²ÒÓ̲Â
Àíîòàö³ÿ. Âèâ÷åíî ïðîöåñ ñóì³ñíîãî îêèñíåííÿ ãóäðîíó
òà ïðîìèñëîâî¿ íàôòîïîë³ìåðíî¿ ñìîëè «Ï³ðîïëàñò-2».
Íàâåäåíî ðåçóëüòàòè åêñïåðèìåíòàëüíèõ äîñë³äæåíü îñíîâíèõ
çàêîíîì³ðíîñòåé ïðîöåñó îäåðæàííÿ íàôòîïîë³ìåðíèõ ñìîë
ç êàðáîêñèëüíèìè ãðóïàìè íà îñíîâ³ ôðàêö³¿ Ñ9 ï³ðîêîíäåí-
ñàòó ï³ðîë³çó âóãëåâîäíåâî¿ ñèðîâèíè. Âñòàíîâëåíî, ùî ñòâîðåí³
íàôòîïîë³ìåðí³ ñìîëè ìîæóòü áóòè âèêîðèñòàí³ äëÿ
ìîäèô³êàö³¿ íàôòîâèõ á³òóì³â.
Êëþ÷îâ³ ñëîâà: ãóäðîí, îêèñíåíèé á³òóì,
íàôòîïîë³ìåðíà ñìîëà, êàðáîêñèëüíà ãðóïà, ìîäèô³êàö³ÿ,
á³òóìíî-ïîë³ìåðíà êîìïîçèö³ÿ.
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 2, No. 1, 2008 Chemical Technology

Vyacheslav Zhyznevskiy and Volodymyr Gumenetskiy

CATALYTIC OXIDATION OF tert-BUTYL ALCOHOL

TO METHACROLEIN
Lviv Polytechnic National University
12 Bandera str., 79013 Lviv, Ukraine
Received: November 12, 2007

Abstract. Oxidation of tert-butyl alcohol (TBA) to diluted with H2SO4, from gases of the catalytic cracking
methacrolein (ÌA) over Fe-Te-Mo-Ox catalyst (Cat), and hydrocarbons pyrolysis.
promoted by Ca(NO3)2 has been investigated. Promoter
concentration, which was optimum by the ÌA yield, has &+&+&+&+&22+
been established (Ca/Mo = 0.05). Using catalyst of such (2)
a type the MA yield was 87.1 % (calculated for supplied
TBA) at the temperature of 663 K, process time of 2.5 s
and TBA concentration of 7.0 % with the concentration
of water vapour in the air of 20 %. Under mentioned
conditions TBA conversion was 100 %, isobutylene
conversion – 95.5 %, selectivity by MA was 87.6 % and
by CO2 – 12.4 %.
Key words: oxidation, catalyst, process, tert-butyl alcohol,
methacrolein, optimization
1. Introduction
MA is the valuable monomer of chemical industry,
used for the production of methacrylic acid (MAA) and
its derivatives. Polymeric materials on the basis of MAA
derivatives are characterized by transparency, chemical
stability and ability to pass through an ultraviolet (UV)
radiation. That is why they are used in the production of
organic glass, glues, light-optical equipment etc.
A present-day production of MAA is based on the
catalytic oxidation of isobutylene (i-C4) but its every year
increase is restrained because of the i-C4 deficit. The main
part of isobutylene is used for the production of
methyltertbutyl ether, which is high-octane component
of petrol in the presence of acid catalysts (reaction 1)
&+

+
&+&&+&+2++&&2&+
&+ &+
Hence, the search of alternative raw material for
MAA and methacrylates production is the issue of the
day, which can be decided, to our opinion, using TBA as
a raw material. The considerable amount of TBA is
obtained by oxidation of propylene oxide to propylene
(reaction 2) and during the extraction of isobutylene,
&+&+&+&+&2+
2
Fe-Te-Mo-Ox reveals good catalytic properties as
a catalyst for the reaction of i-C4 oxidation. The addition
of different promoters, earth-alkali elements in particular,
increases its efficiency in the reaction of i-C4 oxidation
[1]. There are insuffucient literature reports, devoted to
the TBA oxidation. That is why, to our opinion, research
of catalytic properties of above-mentioned catalyst in the
reaction of TBA oxidation and its promotion with different
additives is an actual question.
The aim of our work is the research of Ca2+ nitrate
effect on the catalytic properties of Fe : Te : Mo
(1 : 0.85 : 1) catalyst in the TBA oxidation reaction.
2. Experimental
The following reagents were used for the catalysts
preparation:
(NH4)6Mo7O24×4H2O – ammonium hexamolibdate,
chemically purified;
H2TeO4×2H 2O – ortho-telluric acid, chemically
purified;
Fe(NO3)3×9H2O – ferric nitrate, chemically purified;
Ca(NO3)2 – calcium nitrate, chemically purified.
Corresponding solutions of the above-mentioned
components in distilled water were prepared. Then
(1) catalysts with calculated atomic ratio between metals were
synthesized using calcium nitrate as a promoter. The
procedure of catalysts preparation is represented in [2].
Catalyst phase composition was determined by
X-ray phase technique using DRON-2 diffractometer.
X-ray pictures were decoded using ASTM tables [3].
The specific surface of the catalysts was
determined by chromatographic method of argon thermal
desorption [3].
56 Vyacheslav Zhyznevskiy et al.
The surface acidity of the catalysts was determined
using impulse chromatography of NH3 chemisorption [4].
TBA adsorption over catalyst surface was examined
by impulse chromatography. The column filled with the
catalyst of the known mass was connected with
chromatograph gaseous system and placed into a
thermostat, where it was blown through at 723 K during
1 h. Then the temperature was decreased to the adsorption
temperature and the given impulse volume of TBA was
supplied over the catalyst till the catalyst surface was fully
saturated with absorbate. The saturation was fixed by the
constancy of peak area on the potentiometer of the
katharometer. The amount of the product chemisorbed
by catalyst surface was calculated using known amounts
of supplied and non-chemisorbed TBA.
After the saturation of catalyst surface with the
adsorbate the column was again blown through with helium
till physically adsorbed TBA was removed completely, i.e.
till the chromatograph recorder showed the zero line. Then
the programmed heating of the column was switched on
and TBA desorption heat was determined using two
different detectors – katharomether and flame-ionization
detectors.
Catalytic activity of Fe-Te-Mo-Ox system with
Ca(NO3)2 additives was determined by impulse methods
using “Viruchrom” chromatograph. A reactor with
vibroliquefied catalyst was placed beyond the vaporizer
in such a way that it was possible to disconnect the reactor
in order to prepare the catalyst and maintain its properties.
All reaction products were controlled by detectors
and recorded by potentiometers [2].
3. Results and Discussion
It is known that in the processes of partial oxidation
of organic substances the catalyst activity depends on the
mobility of surface oxygen [5], as well as on acidity and
basicity of catalyst surface [6]. M. Ai [7] considers that
acid centers of Cat surface containing cations with high
electronic inefficiency favor the activation of electron-
donor reagents (olefines, alcohols and others). At the same
time catalysts with optimum acidity have the heightened
selectivity in the processes of incomplete oxidation. On
the basic centers of Cat surface electron-acceptor reagents
are activated, i.e. oxygen is activated in the oxidation
processes. It is also known [1] that at isobutylene oxidation
over Fe-Te-Mo-Ox the stage of active centers reoxidation
is the limiting stage of the process, that is why elements
of basic character (alkaline alkaline-earth ones) may be
promoters to such Cat. Investigated Ca2+ cation belongs
to promoters of above-mentioned type. Its content
(calculated for MA yield) is optimum in the Cat promoted
by earth-alkaline elements.
For the research of cation effect on catalytic
properties of Fe-Te-Mo-Ox the series of Cats with Ca/Mo
different ratio were prepared. Catalytic properties of the
catalysts were studied in a flow reactor with the stationary
Cat and impulse feed of reaction mixture. The impulse
dose was 12.5 cm3 at Cat volume 0.3–2 cm3. Under such
conditions chromatographic complications were absent –
the chromatographic mode of reaction proceeding was
not observed.
The composition of investigated Cats and their
physico-chemical and catalytic properties at the TBA
oxidation are presented in Table 1.
The ÌÀ yield achieves maximum (94.5 %) under
the conditions of reaction proceeding over the Cat while
the Ca/Mo ratio equals to 0.05. Evidently, that over a
non-promoted Cat the MA yield is minimum (42 %)
compared with the Cat promoted by Ca2+. There is a
large yield of products of destructive (acetic aldehyde)
and deep (CO, CO2, H2O) oxidation on an initial contact.
Selectivity by the sum of destructive and deep oxidation
products is over 30 %. The Cat activity is also minor
compared with promoted catalysts, but at small contact
time. However it should be taken into account that
conversion increases but selectivity decreases with the
increase of contact time.
The comparison of i-C 4H8 and TBA oxidation
processes over Fe-Te-Mo-Ox Cat, promoted by earth-
alkaline elements shows the following. The effect of earth-
alkaline promoters on the Fe-Te-Mo-Ox catalytic properties
in the reaction of isobutylene oxidation to MA has been
investigated [10]. It was established that at T = 693 K
and t = 1.4 s the highest yield by MA (86.1 %), XiC4H8 =
99.0 % and SMA = 86.9 % were achieved over the Cat
promoted by Mg (Mg/Mo = 0.1). If the Cat is promoted
by Ca, then under the same conditions the highest yield
by MA (75 %), XiC4H8 = 91.6 % and SMA = 81.9 % were
achieved over the Cat while Ca/Mo ratio equals to 0.05.
Thus, optimum Cats are different for the oxidation of
i-C4H8 and TBA. In the first case the Cat is promoted by
Mg, in the second – by Ca. The Me/Mo ratio is also
different for both cases: Mg/Mo = 0.1 and Ca/Mo = 0.05.
Comparison of the Cat catalytic properties shows
that the surface acidity is maximum on the surface of the
Cat with Ca/Mo = 0.05, which is the best also by MA
yield. It has also minimum parameters of Tm (391 K) and
Ea of NH3 desorption from a surface (68 kJ/mol). The
Cat with the ratio Ca/Mo = 1.0 and the non-promoted Cat
have the least selectivity by MA. The first one has the
minimum acidity (0.3 mmol/m 2) and low Tm (393 K),
practically the same as that of the Cat with the optimum
composition but the amount of active centers of NH3
chemisorption is minimum (0.2·10-18 c/m2) compared with
the optimum Cat (2.8·10-18 c/m2).
 Catalytic Oxidation of Tert-Butyl Alcohol to Methacrolein 57

Table 1
Effect of calcium concentration (Ca/Mo ratio) in Fe-Te-Mo-Ox Cat on its surface acidity and catalytic
properties at the reaction of TBA oxidation
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Notes: NH3 chemisorption at 343 K, Vimp = 0.1 cm3, Vf is feed rate = 0.56 cm3/s; desorption 0.27 K/s, Cat amount related to
SS = 10 m2; Ss is a specific surface up to Cat activation; K is acidity, mmol NH3/m2; Vd is an amount of desorbed NH3, mmol/m2; Tm is a
temperature of maximum desorption peak, K; Ea is activation energy of NH3 desorption, kJ/mol; N is an amount of acid centers on the Cat
surface, c/m2. Catalytic properties (XiC4H8, SMA, BMA) are obtained at T = 663 K, tc = 3.3 s, 5 mol % of TBA in the air.
* for the initial Cat tc = 0.72 s.

Table 2
TBA chemisorption over Fe-Te-Mo-Ox with different ratio of Ca/Mo at 343 K
SS = 2 m2; VHe = 0.4 cm3/s, Vimp = 0.1 cm3
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Notes: Tb, Tm and Te are temperatures of beginning, maximum and end of desorption, K; Ed is activation energy of desorption,
kJ/mol; q is a coverage degree of the surface (depending on a monolayer in accordance with SS and size of TBA molecule cross-section,
calculated using [8]).

At first general surface acidity increases with the
increase of promoter concentration to optimum ratio and
then decreases. High promoter concentrations
considerably increase the specific surface (2.5 m2/g) and
decrease the Cat acidity and activity. The decrease of
selectivity by MA with the increase of Ca/Mo ratio more
than optimum value is connected with the fact that the
promoter disables the active centers of MA formation and
creates the centers of very active oxygen formation.
H H
2H222
The two latter forms (O– and O2–) are very active
in oxidation reaction and mainly form the products of
complete oxidation.
As the reaction of TBA oxidation to MA takes place
by an adsorptive redox mechanism, TBA chemisorption
was investigated over the catalysts promoted with Ca
(Table 2).
It was established that TBA maximum amount
(5.5 mmol/m2) is chemisorbed over the Cat which is the
best by MA yield (catalytic properties are presented in
Table 1). At first till the optimum composition of the Cat,
its adsorption ability by TBA increases with the increase
of promoter concentration and then decreases. The highest
Tm in the I peak of desorption is observed over non-
promoted Cat, then it decreases to the ratio of Ca/Mo =
=0.05–0.1 and increases again in time.
Chromatographic analysis shows that TBA and
i-C 4 are present in the I peak of thermal sorption
(approximately in equal amount) and MA, i-C4, CO and
CO 2 – in the second peak (MA mostly). Maximum
activation energy of desorption of the first form products
(40 kJ/mol) is obtained over the optimum Cat. Values of
T m and T e increase with the increase of promoter
concentration, but Ed and i-C4 concentrations considerably
decrease in products. These Cats have the low surface
58 Vyacheslav Zhyznevskiy et al.
acidity (Table 1), that is why the velocity of NH 3
dehydration to i-C4 is insignificant. For the second peak
the value of Tm is practically equal to the temperature of
heating end of the Cat, which was not heated higher than
723 K, however product Ed is also maximum over the
optimum Cat (83 kJ/mol). At first with the increase of
promoter concentration this value increases and then
decreases. Comparison of centers amount of NH3 (Table
1) and TBA (Table 2) shows that these values are
practically identical. Obviously, under the research
conditions TBA is chemisorbed over every acid center.
Researches of the effect of recovery degree of the
Cat optimum by MA yield (Ca/Mo = 0.05) on its catalytic
properties in the reaction of TBA oxidation show (Fig. 1)
that catalyst activity notably decreases as the catalyst is
recovered. The Cat reduction was carried out by mixture
consisting of 5 % TBA in the air. After the cycling of 44
impulses of recovery mixture (RM) the conversion degree
of isobutylene decreases from 97.0 % to 9.0 % (oxidation
rate decreases from 1.2 to 0.15·10-6 mol·m -2·s -1), and
selectivity by MA, on the contrary, increases from 50 to
83 %. Thus on the graphic chart of selectivity versus
degree of catalyst recovery there is a maximum at the
recovery degree of 4–5 %. The increase of selectivity in
the first impulses of RM is obviously connected with the
removal of the more active surface oxygen, which takes
part in the reactions of complete oxidation. After that a
process selectivity is stabilized.
ecat % SMA, % WiC H , mol % /S
4 8
Impuls amount
Fig. 1. Recovery of Fe-Te-Mo-O Cat, promoted with Ca
(Ca/Mo = 0.05), by mixture of 5 mol % TBA in the air.
Pulse reactor, T = 663 K, Vimp = 5.5 cm3; Vf = 0.55 cm3/s.
1 – velocity of isobutylene conversion, mol/(m 2·s);
2 – selectivity by MA, %; 3 – a degree of oxygen removal,
mass % (e) calculated for the Cat:
0.5Fe2O·MoO3·0.85TeO3·0.05CaO
However different promoters of alkaline-earth
elements influence in a different way the stages of recovery
and reoxidation of promoted catalysts (Table 3). All
promoted catalysts have higher activity and selectivity both
in the first and in the 20th impulse of RM in comparison
with an initial catalyst (C0).
By activity in the 1th impulse of RM they are situated
in the following order:
Ca > Sr > Mg = Ba > Be > C0,
by selectivity in the same impulse:
Sr > Ca = Ba > Mg > Be > C0.
In the 20th impulse by activity:
Ba > Cr > Ca > Mg > Be = C0,
by selectivity:
Ca > Be > Mg > C0 > Sr > Ba.
The obtained results show that addition of alkaline-
earth promoters considerably enhances the mobility of
surface oxygen. Moreover, they lock the active centers
of complete oxidation.
Since catalytic properties of the heterogeneous
catalytic system are determined by its phase composition,
which substantially changes during the change of reaction
mixture composition and conditions of catalyst work, the
corresponding researches were conducted. They showed
that non-promoted catalyst consists mainly of phase of
Fe-Te-Mo-O triple compound and ordinary ferric molybdate.
The catalyst promoted with Ca consists of a triple compound,
MoO3, Fe2O3 phases and minor amount of ferric molybdate.
After the recovery of this catalyst by the mixture of isobutylene
and the air its phase composition differs from the
nonrecoverable catalyst by the presence of molybdenum
recovery phases – mainly Mo9O26. After its reoxidation by
oxygen it does not return to the initial state. After work of
the catalyst with an optimum composition (Ca/Mo = 0.05)
in the flow reactor during about 10 h it consists mainly of a
triple compound phase and Fe2(MoO4)3, as well as initial
non-promoted catalyst. Catalysts with higher content of Ca
(Ca/Mo = 1.0; 2.0) have mainly a phase of Ca molybdate
and they are inactive in a reaction of TBA oxidation to MA.
Thus, the phase of a triple compound of
Fe-Te-Mo oxides with the slight excess of MoO3 is the
active phase of Fe-Te-Mo-O Cat. MoO3 dissolves in the
main phase and causes defectiveness of its structure which
favors the formation of oxidation active centers.
3.1. Mechanism and kinetics of TBA
oxidation to MA over an optimum
catalyst
On the basis of that the process of TBA oxidation
over this catalytic system (Ca/Mo = 0.05) takes place by
phasic redox mechanism, which is confirmed by the
results of researches (Fig. 1), Mars-van-Krevelen
approach which is widely applied for the description of
reaction rates of olefins partial oxidation [6] was used for
the derivation of kinetic equations.
 Catalytic Oxidation of Tert-Butyl Alcohol to Methacrolein 59

Table 3
Recovery and reoxidation of Fe-Te-Mo-O Cats promoted by the cations of alkaline-earth metals,
with optimum ratio Me/Mo (by MA yield) in the pulse reactor
Vimp = 0.71 cm3, Vf= 0.56 cm3/s, total surface of the Cat – 10 m2
7RJHWKHUIRU ,QWK
WKLPSXOVHRI50 WKLPSXOVHRI50
66 LPSXOVHV LPSXOVH
0H0R
PJ 9 0$ 9 & 9 2 9 & 9 2 9 2 9¶2 RI20
:Â 60$ 
:Â  60$
FP FP FP FP FP 50  20  9¶2
²             
%H             
0J             
&D             
6U             
%D             
Notes: W – conversion rate of isobutylene, mol/(m2·s); VMA – a volume of formed MA, cm3; VC4 – a volume of reacted isobutylene,
cm ; VO2 – a volume of removed oxygen, cm3; V’O2 – a volume of absorbed oxygen at the feed of oxidazing mixture, cm3; Vimp – an impulse
3

volume, cm3;Vf – feed rate, cm3/s; OM – oxidizing mixture.

 >2@U0$
N>5+ @ ˜ N  >2  @ 
U (3)
QN>5+ @  N  >2  @ 

where k1, k2 are rate constants of the recovery and 
reoxidation of catalyst surface centres, correspondingly; 
n is a stoichiometric coefficient by oxygen, for the reaction
of MA formation, n = 1.  
For the determination of k1 and k2 equations result  
in linear view:

>2  @   >2 @
 ˜  . (4) 
U N  N >5+ @

Researches are carried our in the kinetic area of           
reaction proceeding, that was confirmed by crushing the >2@>L&+@
catalyst grains and changing the stream linear velocity at
Fig. 2. Dependence of [O2]/rMA on [O2]/[i-C4H8] for the
T = 623, 643 and 663 K.
reaction of MA formation by TBA oxidation at different
Since the TBA oxidation will be realized in industry
temperatures. Recation conditions for the Figs. 2–4:
at large excess of O2 (5 mol % TBA in the air), we supported pulse reactor, Vimp = 5.5 cm3; Vf = 0.55 cm3/s, tc = 1.25 s
the high and permanent concentration of O 2
(~8.0·10–3 mol/dm3) during the kinetics research; the TBA of these stages (k i ) and adsorption heat (b i ) were
concentration was changed from 0.2 10-3 to 2·10-3 mol/dm3. determined (Fig. 3).
The obtained results show that the increase of Comparison of the stages constants shows that the
isobutylene concentration (TBA in all experiments reacted stage of catalyst recovery in the reaction of MA formation
fully) increases selectivity of MA formation at all explored has a higher rate comparatively with the stage of catalyst
temperatures, however olefins conversion decreases. The reoxidation, in spite of oxygen excess in the reaction
olefin high concentrations miserably affect the selectivity mixture. Obviously the reoxidation stage is a limiting stage
by MA, and at low concentrations the selectivity notably that was also observed over a non-promoted catalyst
decreases with the increase of temperature. Reaction rates during TBA oxidation to MA. Comparison of activation
of all oxidation products formation increase with the energies of the limiting stage of the TBA oxidation to MA
increase of concentration and temperature. and effective activation energy of isobutylene oxidation
Dependence of [O2]/rMA on [O2]/[i-C4H8] allows to to MA over the non-promoted catalyst shows that higher
determine the constants of the recovery and reoxidation activation energy of oxidation (150 kJ/mol) is observed
stages of the catalyst at all explored temperatures (where at TBA oxidation compared with isobutylene oxidation
[O2] is a concentration, r is formation rate (Fig. 2)). (130 kJ/mol). Probably there is a competition for an active
Using dependence of rate constants upon surface between isobutylene and water vapour which
temperature in the lnki®1/T coordinates activation energies appears during TBA hydration.
60 Vyacheslav Zhyznevskiy et al.

OQNLEL


E&2


E&2



N0$

N 0$




N&2

N&2
 7±.±
     

0$
Fig. 3. Dependence of lnki (bi) upon 1/T: N  and N 0$  are constants of MA formation stages;
kCO, kCO2, bCO and bCO2 are rate constants and adsorption coefficients of CO and CO2 formation by TBA oxidation

OQNLEL


E&2
E&2
E&2
 
E&2




  



N&2

   N&2
N&2
N&2
 7±.±
               

Fig. 4. Dependence of lnki(bi) upon 1/T:

for the reaction of MA oxidation (O) and isobutylene (£ ) into CO and CO2
 Catalytic Oxidation of Tert-Butyl Alcohol to Methacrolein 61

The following parallel-serial scheme has been The equation constants and adsorption coefficients
proposed for the formation of deep oxidation products were determined by a graphic method (Figs. 5 and 6),
using the results of kinetics investigation. their values are resulted in Tables 5 and 6.
L&+0$ It should be noted that acids (acetic, methacrylic)
N were also formed during MA oxidation, however only
N N formation rates of ÑÎ and CO2 were taken into account.
During the calculations of rate constants of CO
&2&2 and CO2 formation from isobutylene the formation rate of
For the determination of k3/k4 ratio kinetics of MA these products from MA were calculated depending on
oxidation over the optimum catalyst was investigated the concentration of the latter in the reaction mixture. Then
(Table 4). this calculated rate was subtracted from a total rate. Using
It is accepted that the reaction of CO and CO2 graphic method rate constants and adsorption coefficients
formation takes place between an organic reagent adsorbed of CO and CO 2 formation from isobutylene were
on the surface of the catalyst and oxygen of a gas phase. calculated by the difference between the total rate and the
In such a case the reaction rate can be described by the rate of CO and CO2 formation from ÌÀ.
equation given below [9]: On the basis of above-mentioned researches the
ratio between constants of consecutive (k2) and parallel
. F E F >5+ @>2  @ (5)
UF (k3) ways of formation of isobutylene oxidation products
  E F >5+ @
have been calculated. It is established that for the reaction
of CO2 formation from isobutylene or MA ki constants
where rc is a gross-rate; Kc is a total constant; bc is are practically identical at all temperatures and effective
a total adsorption coefficient; [RH] = [iC4H8] + [MA]. constants (kibi=kef) are practically identical at 663 K. At
This equation in a linear aspect is the following: low temperatures (623 K) more CO2 is formed by consecu-
>2  @   tive MA afteroxidation. For the reaction of CO formation
 (6)
UF . F . F E F >5+@ ratio N &20$
 N L&
FR
 increases with the decrease of tempe-
rature and kef, on the contrary, decreases, that testifies to
predominant CO formation from MA at high temperatures.
Table 4
Methacrolein oxidation in ÑÎ and CO2
SS = 0.6 m2/g, pulse reactor, Vimp = 5.5 cm3; Vf = 0.55 cm3/s, tc = 1.25 s
> @Â >2@Â >&2@Â > @Â :&2Â :&2Â ;
7.
PROO PROO PROO PROO PROO PROO 
      
      

      
      
      
      

      
      
      
      

      
      

Table 5
Values of rate constant, adsorption coefficient and activation energy
of TBA oxidation to MA, CO and CO2
  
 
NV NV .FÂV %FOPRO .FÂV %FOPRO
      
      
      
“N-PRO      
62 Vyacheslav Zhyznevskiy et al.

Table 6
Values of rate constant, adsorption coefficient and activation energy of ÌÀ (1)
and isobutylene (2) oxidation into ÑÎ and ÑÎ2

     
  NÂ E NÂ E NÂ E NÂ E
NN NN
V OPRO V OPRO V OPRO V OPRO
          
          
          
“
        ² ²
N-PRO
     
 DQGE  Â  Â  Â   Â   Â  Â  ² ²

Note: k4/k5 - constant ratio between consecutive and parallel ways of CO and CO2 formation

 >2@U V

 






  
 Fig. 5. Dependence of [O2]/rCO2 upon 1/[RH]
  for the reaction of CO2 formation

by TBA oxidation at different temperatures



    
>5+@Â OPRO
±

 >2@U V

 




  

  Fig. 6. Dependence of [O2]/rCO upon 1/[RH]
for the reaction of CO formation by TBA
 oxidation at different temperatures




    
>5+@±OPRO
 Catalytic Oxidation of Tert-Butyl Alcohol to Methacrolein 63

Thus, formation rates of isobutylene oxidation products formed from TBA, can be described by the following
kinetic equations:
 ˜  ˜ H[S  7  ˜ >L& +  @ ˜ >2 @
U0$ (7)
 ˜ ˜ H[S  7  ˜ >L& +  @   ˜  ˜ H[S  7  ˜ >2 @

 ˜ ˜ H[S  7  ˜ > 0$@ ˜ >2 @  ˜ ˜ H[S  7  ˜ >L& +  @ ˜ >2 @ (8)
U&2 
   ˜ ˜ H[S  7  ˜ > 0$@    ˜ H[S  7  ˜ >L& +  @

 ˜   ˜ H[S  7  ˜ > 0$@ ˜ >2 @  ˜ ˜ H[S  7  ˜ >L& +  @ ˜ >2 @ (9)
U&2 
   ˜ H[S  7  ˜ > 0$@
4. Optimization of the Process
Optimization of the process was carried out on the
basis of the obtained kinetic model at temperatures of 643,
673, 693 K and initial concentrations of isobutylene (TBA)
in the air of 2.5 and 7.0 mol %. It is established that the
maximum MA yield (87.5 %) is obtained at 643 K, the
initial concentration of i-C4 (TBA) 7 mol % and contact
time 4.4 s. With the increase of temperature the MA yield
decreases from 87.5 % (643 K) to 84.1 % (693 K). At the
same time the contact time is twice greater at 643 K
(4.4 s against 2.2 s). At 673 K and i-C4 concentration 7
mol % the isobutylene conversion is practically complete
(X = 99.5 %) at = 2.5 s. Selectivity by ÌÀ is 87.6 %,
yield is 87.1 %. Selectivity by CO2+CO is 12.4 % while
adding water vapour (20 mol %) to the reaction mixture.
It is established that water vapour accelerates a reaction,
preventing the formation of high molecular polymerization
or pyrolysis products on the surface, and increases
selectivity by ÌÀ.
So optimum conditions are the following:
[i-C4] = 7 mol % in the air + 20 mol % of water vapour;
T = 673 K; ÕTBA = 100 %, XiC4 = 99.5 %, SMA = 87.6;
ÑÎ + CO2 = 12.4 %. ÌÀ yield is 87.1 %.
References
[1] Zhyznevskiy V.: Kataliticheskoe okislenie nizkomolekulyarnyh
olefinov. PhD.thesis 1982
   ˜ ˜ H[S  7  ˜ >L& +  @
[2] Gyznevskiy V., Gumenetskiy V., Bagan L. and Majkova S.:
J. Phys.Khimii, 2001, 75 (10), 1782.
[3] Reiter V (ed.): Problemy teorii i praktiki issledovanij v oblasti
kataliza. Naukova dumka, Kyiv 1973.
[4] Navalihina M., Romanovskiy B., Topchieva K. and Demin
V.: Kinetika i kataliz, 1972, 13, 341.
[5] Golodec G.: Heterogenno-kataliticheskie reakcii s uchastiem
molekulyarnogo kisloroda, Naukova dumka, Kyiv 1977.
[6] Boreskov G.: Kinetika i kataliz, 1970, 1, 5.
[7] Ai M.: J. Catalysis, 1978, 1, 16.
[8] Brunauer S.: Adsorbciya gazov i parov, Moskva 1948.
[9] Bremer G. and Vendlandsh K.: Vvedenie v heterogennyj
kataliz. Mir, Moskva 1981.
[10] Dvonchova E.: PhD thesis, Lviv 1988.
ÊÀÒÀ˲ÒÈ×ÍÅ ÎÊÈÑÍÅÍÍß
ÒÐÅÒÁÓÒÈËÎÂÎÃÎ ÑÏÈÐÒÓ
ÄÎ ÌÅÒÀÊÐÎËůÍÓ
Àíîòàö³ÿ. Äîñë³äæåíî ïðîöåñ îêèñíåííÿ òðåò-
áóòèëîâîãî ñïèðòó (ÒÁÑ) äî ìåòàêðîëå¿íó (ÌÀ) íà
Fe-Te-Mo-Ox êàòàë³çàòîð³ (Êò), ïðîìîòîâàíîìó Ca(NO3)2.
Âñòàíîâëåíî îïòèìàëüíó çà âèõîäîì ÌÀ êîíöåíòðàö³þ
ïðîìîòîðà (Ñà/Ìî = 0,05). Íà êàòàë³çàòîð³ òàêîãî òèïó
âèõ³ä ÌÀ íà ïîäàíèé ÒÁÑ ïðè Ò = 663 Ê, tê = 2,5 ñ ñòàíîâèòü
87,1 %, ïðè êîíöåíòðàö³¿ ÒÁÑ 7,0 % ó ïîâ³òð³ ç 20 % ïàðè
âîäè. Çà öèõ óìîâ êîíâåðñ³ÿ ÒÁÑ 100 %, ³çîáóòèëåíó – 95,5 %,
ñåëåêòèâí³ñòü çà ÌÀ – 87,6 %; çà ÑÎ2 - 12,4 %.
Êëþ÷îâ³ ñëîâà: îêèñíåííÿ, êàòàë³çàòîð, ïðîöåñ, òðåò-
áóòèëîâèé ñïèðò, ìåòàêðîëå¿í, îïòèì³çàö³ÿ.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 1, 2008
Anatoliy Starovoit and Yevgen Maliy
RESEARCH OF POLYMERIC ADDITIVE INFLUENCE
OF ORGANIC COMPOSITION ON THERMOCHEMICAL CONVERSION
OF CARBON MASSES
National Metallurgical Academy of Ukraine
4 Gagarina av., 49000 Dnepropetrovsk, Ukraine
ukrkoks@a-teleport.com
Received: November 11, 2007
Abstract. The influence of polymeric additives on
properties of carbon masses of self calcinating electrodes
in their carbonization process has been investigated. It
has been found that polymeric additive intensifies the
interaction of carbon filler with an electrode pitch – the
binding agent – that is represented with high quality on
thermographic characteristics of laboratory masses. The
mechanism of components interaction with a modifier
has been formulated.
Key words: carbon mass, thermoanthracite, coal pitch,
wetting angle, filler, binding agent, carbonization,
polymeric additive.
1. Introduction
Ukraine is one of the CIS countries, where the
world production of coal-graphite goods equals to about
2.5 million ton per year, from which about 65 % are
electrodes for steel production, ferro-alloys, corundum,
fibrous structure and others [1].
The specific consumption of electrodes which
consists of evaporation, erosion (in the arc area), oxidation
and destruction of its working surface in the candle area
is the major characteristic of electric furnace steelmaking.
The forming of electrode properties complex is
characterized by the set of factors and, first of all, by the
properties of initial raw material components, and by the
processes of their joint interaction at different stages of
carbonization. Physico-chemical processes in the “filler-
binder” system condition operational characteristics of
the final item [2].
Carbon masses, used for the production of electrodes,
anodes, graphite blocks and other products are the mixtures
of hard carbon fillers (thermoanthracite, graphite, various
cokes and others) with the binding agent – pitch.
Requirements to the raw material properties and to
the coal pitches in particular are always conditioned by
Chemical Technology
basic functions which they fulfill in carbon mass. On the
whole the influence of the electrode pitch on the process
is more effective when it possesses a high adhesion and
sintering ability, low ash content and yield of volatile
components, optimum content of substances insoluble in
toluene and quinoline, as well as ability to give a high coke.
In this connection the development of technological
approaches capable of taking into account the instability of
coal resin quality to provide the obtaining of electrode pitches
with the promoted operational properties is very actual.
It should be noted that basic directions in area of
pitch production are: i) obtaining of the binding agents of
stable quality with the narrow changeable interval of
indexes; ii) obtaining of rather wide gamut of pitches taking
into account the technological features of different
electrodes production.
To our opinion, the second direction is the decision
of constantly arising problems because it gives the possibility
to provide users by the pitch of necessary quality.
2. Experimental
Research of dominant partner of binding agent was
carried out using thermal analysis and method of wetting
angle determination. The wetting angle between a pitch
and thermoanthracite was determined by the method of
mapping the megascopic image of the drop on a screen.
The complex thermal analysis was carried out using
the D-1500 derivatograph produced by the “MOM” firm
in the argon atmosphere within the temperature range of
293–1073 Ê with the heating rate 278 Ê/min. The alumina
served as a standard.
3. Results and Discussion
Aspiration for improving operational properties of
electrode pitch in relation to carbon materials which
66 Anatoliy Starovoit et al.
characterize its quality in the best way, explained the variety
of yielding pitch additives of organic origin [3-5].
It is assumed in work [6] that at modification of
raw A (main substance) by the by-product B (modifying
additive) some reasons of component A pyrolysis
intensification are marked:
- substance B, reacting with A, improves the
solubility and the softening temperature of the latter or its
derivatives due to moving of hydrogen atoms or
hydrocarbon group from B to A;
- substance B participates in the formation of pitch
liquid phase, which is formed by A. Furthermore the
molecules in main substance form a liquid-crystal phase with
difficulty that results in the formation of the stratified structure
on the basis of molecules consisting the liquid crystals. At
the same time the mass transfer processes are accelerated;
- substance B in the mass transfer reactions serves
as the catalyst, providing the growth of permolecular
formations of the pitch unequigranular system of the pitch;
- association of permolecular compounds in clusters
grows steadily due to interaction of additive B and the modified
substance A that promotes anisotropy and predetermines the
development of intermediate products structure.
The authors of work [7] note that the small quantity
of additive within the limits of 5–15 % furthermore can
provoke the system to the substantial changes of
Composition of polymeric additive
'LPHWK\O
$ HWRSKHQH $FHQDSKWHQH
QDSKWKDOHQH
microstructure of the coke residue. So, using different
organic additives and methods of their preparation, the
cokes with different anisotropy of structure (5–200 mcm)
were obtained.
These data find their confirmation in work [8],
where additive contribution of additives is shown in
forming main properties of coke residue and the substantial
role of “dominant partner” effect is underlined.
As carbonization of carbon masses is a complex
thermochemical process accompanied by the group of
parallel-consecutive reactions, it was necessary to study the
mechanism of polymeric additive influence (Table 1), both
on the binding agent (Table 2) and on the filler (Table 3).
3.1. The method of “lying drop”
Using the method of “lying drop” [9] it is possible
to fix such physical phenomenon, as wetting angle.
However, for achievement of the set purpose the method
was updated. Modernization consisted of introduction of
polymeric additive in the quality of “pseudo” layer locating
on the border-line of interface in the “filler-binding agent”
system.
The results of thermal interaction between a drop
of investigated binding agent with a filler surface are
represented in Fig.1.
Table 1
'LSKHQ\OHQH 0HWK\O
)OXRUHQH 5HVLQ
R[LGH QDSKWKDOHQH
PDVVSDUWV
      WKHUHVW


Table 2
Indexes of binding agent properties

6XEVWDQFHVLQVROXEOHLQ <LHOGRIYRODWLOH
0DWHULDO $VK
TXLQROLQH WROXHQH VXEVWDQFHV
(OHFWURGHSLWFK    
*267 d ± ± d

Table 3
Indexes of filler properties

<LHOGRIYRODWLOH
0DWHULDO 6XOSKXU 0RLVWXUH $VK
VXEVWDQFHV
7KHUPRDQWKUDFLWH    
*267 d d d d
 Research of Polymeric Additive Influence of Organic Composition on Thermochemical Conversion... 67

D    E     F ,

D E F ,,
Fig. 1. Character of thermal interaction of pitch drop with hard surface of thermoanthracite (I) and thermoanthracite
with additive (II) at the stove working area temperatures (K): 373 (a), 413 (b), 726 (c)

Resulting from the obtained values of wetting angles of this period at 488 K. The fact of increase of the period
in relation to the modified surface of thermoanthracite, of carbon mass staying in the plastic state when
one can say that polymeric additive changes the character confronted with the less losses of weight testifies to the
of khemosorption processes, interactions with the binding stabilization of forming fragments of initial pitch structure.
agent and more probably all it will be revealed while forming Such a supposition is confirmed by the DTA curve.
the electrode structure. On the first stage until the temperature of the
beginning of destruction determined by the DTA curve, the
3.2. Thermal analysis mass loss with additives is less, than that of initial carbon
mass, and rate of loss is lower. On the second stage of
Such an influence is more evidently reflected on conversion the loss mass rate of experimental carbon mass
thermochemical conversions of the binding agent in the is higher compared with the initial sample. On the third and
carbonization process of carbon mass for self-calcinating fourth stages the rate decreases again, although the mass
electrodes (Fig. 2). loss on these stages predominates a little bit.
One can see on the DTA curve (b) presenting pitch Such a supposition is based on the results of
composition with modified filler (4 %) the period of carbon derivatograph analysis. The analysis of initial and
mass staying in the plastic state increases from 503–528°K experimental carbon masses thermogrames was conducted
to 493–533 K compared with initial carbon mass (à), and according to the methodic [10]. The results are given in
the additive amount of 6 % (c) causes the displacement Table 4.
Table 4
Thermographical characteristics of carbon mass carbonization
5DWHRIPDVVORVVDWWKHWHPSHUDWXUH
7HPSHUDWXUHLQWHUYDO. 0DVVORVV
6DPSOHV LQWHUYDO

, ,, ,,, ,9 , ,, ,,, ,9
,QLWLDO
± ± ± ±     

0RGLILHGE\
± ± ± ±     
DGGLWLYH
0RGLILHGE\
± ± ± ±     
DGGLWLYH
68 Anatoliy Starovoit et al.


D

F

Fig. 2. Thermogrames of carbon mass (à) and masses modified by polymeric additive: 4 % (b), 6 % (c)
 Research of Polymeric Additive Influence of Organic Composition on Thermochemical Conversion...
Estimating the results of the research on modification
of filler solid surface, one can state, that a new surface
appears on the contiguous areas of carbon material and
additive, that changes liophilno-liophobny properties of the
filler. On the one hand it results in the temperature decrease
of positive wetting angle, and on the other hand – at
temperatures higher than 473 K the modified filler is the strong
catalyst of thermochemical conversions of the binding agent.
4. Conclusions
Thus, on the basis of the carried out experiments
the mechanism of comodifying additive carbonization with
a pitch and carbon mass in the process of the thermal
heating can be represented in two ways.
On the one hand, the additive before the transition
of pitch to the viscidly-fluid state facilitates the process of
its macromolecules attraction and extends the temperature
interval of mesophase origin. On the other hand due to
adhesion forces the additive is disposed and fixed on the
surface of pitch macromolecules. The forming gas-vapor
products of pitch are forced to pass through the film.
Obviously, a nascent adsorption layer from a polymeric
mixture is in some way a barrier or filter, because it traps
gas-vapor products and partly dissolves them. Further the
additive interacts with permolecular compounds, penetrating
into the depth of the pitch. Thus the yield of pitch liquid
mass increases and the viscidity decreases. If the above-
mentioned mechanism is to be examined in the “binding
agent–filler” system, then this effect will be going on until
the establishment of the equilibrium between the surface of
solid carbon material and the binding agent, that in its turn
should intensify wetting, adsorption and adhesion, increasing
the yield of the coke residue and the baking properties of
electrode pitch of the binding agent.
69
References
[1] Pityulin I.: Nauchno-tehnicheskie osnovy sozdaniya
uglerodistyh materialov dlya krupnogabaritnyh electrodov.
Kharkov 2004.
[2] Privalov V. and Stepanenko Ì.: Kamennougolnyi pek.
Metallurgiya, Moskva 1981.
[3] Kremer H.: Chemistry and industry, 1982, 18, 702.
[4]Alscher A. and Wildforster R.: Proceedings of the technical
sessions by the TMS Light Metals Committee at the 118 TMS
Annual Meeting, Las Vegas, Nevada, 1989, 473.
[5] Stepanenko Ì.and Privalov V.: Koks i khimia, 1983, 11, 32.
[6]Marsh H., Mochida I. and Scott E.: Fuel, 1980, 7, 517.
[7]Mochida I., Amamodo K., Maeda K. et al.: Fuel, 1978, 57,
225.
[8] Yegorov V.: Koks i khimia, 1997, 3, 25.
[9] Dyåyåv À.N. et al.: Construction materials on the basis of
graphite, 1969, 4, 51.
[10] Gluschåncî I.: Thermal analysis of hard fuels.
Metallurgiya, Moskva 1981.
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ç ìîäèô³êàòîðîì.
Êëþ÷îâ³ ñëîâà: âóãëåöåâà ìàñà, òåðìîàíòðàöèò,
êàì’ÿíîâóã³ëüíèé ïåê, êðàéîâèé êóò çìî÷óâàííÿ, íàïîâíþâà÷,
çâ’ÿçóþ÷å, êàðáîí³çàö³ÿ, ïîë³ìåðíà äîáàâêà.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No 1, 2008
Tamara Perekupko, Yaroslav Kalymon and Kostyantyn Blazhivsky
DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF INORGANIC
SUBSTANCES: THE PAST, THE PRESENT, THE FUTURE
Lviv Polytechnic National University,
12 Bandera Str., Lviv, 79013, Ukraine
blazhivskyi@gmail.com
Abstract. On the occasion of the 140th anniversary of
the birth of professor, doctor of honoris causa and the
Honoured professor of Lviv Polytechnic, former head of
Department I. Moscicki as well as 70th birthday of
professor, Doctor of Engineering, Honoured professor of
Lviv Polytechnic and present head of Department
V. Yavorsky a short review of the history of the Department
of chemistry and technology of inorganic substances, its
present days, and prospects has been made.
Keywords: history, department, technology of inorganic
substances, technical electrochemistry.
2007 will be remembered by the staff of our
Department by 140th anniversary of the birth of professor,
doctor of honoris causa and the Honoured professor of
Lviv Polytechnic, former head of Department I. Moscicki
as well as 70th birthday of professor, Doctor of
Engineering, Honoured professor of Lviv Polytechnic and
present head of Department V. Yavorsky. To the glorious
anniversary of I. Moscicki article [1] was devoted, where
the life story of this prominent scientist and public man
was widely expounded. However, insufficient attention,
in our view, was given to his role in setting up and
development of our Department in particular and Lviv
Polytechnic on the whole. We consider it as our duty to
reveal in detail an important contribution of these majestic
figures to the achievements and successes of the
Department and doing a short excursus in its history
describe the Department’s present days and prospects.
The history of our Department begins in the remote
19th century, when by the regulation of Tsisar of the
Austria-Hungary Empire on June 18, 1871 three new
Departments were opened in Lviv Technical Academy: of
construction, geodesy and chemical technology. On July
16, 1872 Herman Gunsberg became the first head
(professor) of the Department of chemical technology. In
his capacity as an assistant (from 1857/1858 academic
year) and as an adjunct of Department of general and
technical chemistry (starting from 1863) he was teaching
chemical technology and organized a laboratory [2, 3]. In
full value the Department of chemical technology began
to function from the beginning of 1872.
I
History
Prof. G. Gunsberg taught such courses as
technology of water and fuel, mineral raw material, soda
trade, technology of fats lighting, building materials
production, chemical-engineering analysis, products of
chemical technology, etc. Being the Dean of the Department
of technical chemistry in 1874/1875 and 1875/1876
academic years, he fit out the newly built chemical building
(now the 9th building of the University), which up to now
strikes us by the cleanness of its architectural forms, which
were renewed in 2003. Prof. G. Gunsberg was also an
actual member of the Economic Society of Galicia and
Head of the School of alcoholic production.
After his death in 1879 the Department was headed
by Juliusz Bruhl – Doctor of Philosophy and associate
professor of the Department of chemistry of Aachen
Polytechnic School. In Lviv he began to teach chemical
technology from January 1880 first as a suplent, and since
August 1880 as a professor of chemical technology. Prof.
Yu. Bruhl taught the following courses:
– chemical technology (part I on the 3d year of the
study), which included technology of water, sulfur, sulfuric
and nitric acid, as well as soda trade. As chemistry was
not specialized at that time, this part also included technology
of fuel and illumination materials, production of matches,
metallurgy of iron and zinc, production of ceramics and
glass;
– chemical-engineering analysis (on the 4th year of
the study);
– chemical technology (part II on the 4th year of
the study), which in addition to productions of food
products, glue and soap also included one of the main
courses read to the students of speciality “Chemical
technology of inorganic substances” these days –
production of artificial fertilizers;
– products of chemical technology and their analysis.
After a long illness in 1883 prof. Yu. Bruhl left the
Department and moved to Heidelberg. From 1885 Bron³slav
Pavlevski, who in the years 1881-1882 worked as an
assistant of the Department, in 1882 defended doctoral
thesis in chemical technology and lectured replacing the ill
prof. Yu. Bruhl, became the new head of the Department
of chemical technology. In 1885 B. Pavlevski was given
the rank of professor extraordinary, and since 1888
 Tamara Perekupko et al.
professor ordinary. In 1883-1891 B. Pavlevski managed
the oil researches station. For several times he was elected
a Dean of Department of technical chemistry, and in the
academic years 1896-1897 and 1909-1910 a rector. Prof.
B. Pavlevski was a well-known scientist with profound
many-sided knowledge, extraordinarily hard-working, and
the author of numerous works, which were published in
the country and abroad. His works in the following fields
are known: organic chemistry, geology of mining (for
example, analysis of zinc-tin ores, ozocerite in Truskavets,
mineral waters in Busk, kaolin and peat of Galicia, Bokhen
salt structure, etc), brewing and so on.
Prof. B. Pavlevski, like his predecessors, at first
also taught the whole chemical technology, both inorganic
and organic, but later he passed a part of the courses to
his collaborators. In the last years of his work he lectured
such disciplines as:
1. Chemical technology, part I (for the third year
students), which included metallurgy of iron, zinc, tin,
lead, copper, and other rare metals (aluminum, sodium,
silver, gold, nickel, and other); important alloys and their
properties; chemical technology of such inorganic
substances as sulfur and its compounds, sulfites, sulfuric,
hydrochloric and nitric acid, rock-salt, soda, borax, chlorine
and bleaching substances, potassium chlorate, salts of
ammonium and cyanides, salts of aluminium and chrome.
This course also included technology of ceramics, glass
wares, liquid glass, and matches.
2. Chemical technology, part II (for the third year
students), including sugar refining, soap, candles and
margarine production from fats; production of glue,
gelatine and protein; essential oils and soft resin, lubricants,
and varnishes; production of food products.
3. Chemical technology, part III (for the fourth year
students): production of alcohol, yeasts, beer, vinegar,
starch, dextrin, and glucose.
4. Products of chemical technology and their
analysis.
In 1904 the Department of chemical technology
was parted to the Department of chemical technology I,
which prof. B. Pavlevski continued to lead, and Department
of chemical technology II (agriculture products
processing) and microbiology chaired by prof. Victor
Sinevski, a former student of prof. B. Pavlevski.
From 1885 Prof. B. Pavlevski was a member of
Regional Industrial Council and Regional Mining Council,
in the years 1895-1916 – a counselor of Lviv and Head of
Municipal Technical Commission, in years 1893-1899 –
editor of the Technical magazine and held many high posts
in public and state organizations. Prof. B. Pavlevski passed
away on January 29, 1917.
Upon his departure Ignacy Moscicki, with whose
name formation and development of chemical industry of
Poland of that time are connected, became the head of the
Department of chemical technology. He started his
II
scientific activity in electrotechnology (electro-physical
researches, fixing of atmospheric nitrogen, creation of
condensers of high tension, etc), the methods which he
successfully used in the chemical technology of fixed
nitrogen compounds. In 1910 in Switzerland Prof.
I. Moscicki started a factory of nitric acid by an electro-
thermal method. Prof. I. Moscicki made a lot of scientific
discoveries and became a known scientist.
In 1912 the Senate of Polytechnic School in Lviv
offered I. Moscicki to organize the Department of physical
chemistry and technical electrochemistry and gave him
the title of professor ordinary. I. Moscicki, in spite of his
material well-being in Switzerland, accepted this offer and
for his own money bought and brought to Lviv a few tons
of equipment and machines for the laboratory. Prof.
I. Moscicki started by reading the course of physical
chemistry to 1 and 2 years students on the Department of
technical chemistry. But, since the basic direction of his
researches was chemical technology, in 1924 Prof.
I. Moscicki passed this course to his successor T. Kuczynski,
while continuing teaching the following courses:
1. Chemical technology, part Ia (on the 2d year of
the study), which included technology of water and fuel,
building materials, ceramics, and glass.
2. Chemical technology, part Ib (on the 2d year of
the study), in which rock-salt, salts of potassium; sulfur,
sulfuric, hydrochloric and nitric acid; soda; chlorine;
ammonia; artificial fertilizers; mineral paints; major chemical
preparations; metallurgy were taught.
3. Technical electrochemistry (on the 4th year of
the study), where the electrochemical methods in basic
chemical industry were studied.
Under the direction of prof. I. Moscicki the
laboratories of technical electrochemistry and chemical
technology were equipped on the Department and on 1921
the Department was renamed to the Department of
chemical technology I (large inorganic industry) and
technical electrochemistry. Hence, a special merit of prof.
I. Moscicki consists in the fact that he was the first to
understand closeness and direct connection between
inorganic technology and technical electrochemistry and
the first to combine them within one Department.
During his work on the Department prof.
I. Moscicki elaborated the plans of building a large factory
of nitric acid, ammonium nitrate, and cyanic hydrogen
production, but since the First World War break out they
were never realized. In the academic year 1914-1915
because of the War the studies at Lviv Polytechnic School
was deferred, and from 1915 to 1919 only separate
departments were functioning. In the academic years 1915-
1916 and 1916-1917 prof. I. Moscicki was Dean of the
chemical Department and he never stopped his active
scientific activity. In 1916 he organized a society called
“Methane”, which was concerned in patenting and
introduction of chemical technologies and developing the
 Department of Chemistry and Technology of Inorganic Substances: the Past, the Present, the Future
chemical industry in Galicia in general. In 1917 “Methane”
began to publish the magazine with the same name which
was changed to “Chemical industry” in 1920.
In 1922 prof. I. Moscicki initiates relocation of
“Methane” society to Warsaw, where it was reorganized
to Chemical Research Institute. The main directions of his
researches were rectification of oil, electrolysis of NaCl
and KCl, obtaining of CCl4, production of HCl, distillations
of coal and peat and other. The researches of obtaining
sulfuric acid from gypsum have been launched.
From 1922 to 1925 I. Moscicki was general director
of the large factory of ammonia and its derivatives, which
he finished building in Khozhov. At the same time he
remained the head of the Department at Lviv Polytechnic
School.
In 1922 prof. I. Moscicki was given the title of
Doctor of honoris causa of Lviv Polytechnic. In 1925 he
was elected the Rector of Lviv Polytechnic, but did not
hold this position for long as on 2 Junes, 1926 I. Moscicki
was elected the President of Poland. In this year he was
given the title of honorary professor of Lviv Polytechnic.
Prof. I. Moscicki is the author of over 60 scientific works
and about 40 patents. He was the head of many
organizations and chemical societies, Doctor of honoris
causa of Lviv and Warsaw Polytechnic as well as
universities of Vilnius, Frayburg, Tartu.
When prof. I. Moscicki became the President of
Poland Tadeush Kuczynski took over the post of the
Department’s chair. Prior to this (1920-1922) T. Kuczynski
worked as the head of the research laboratory of mineral
oils factory in Drohobych, later as a leading chemist and
technical director of “Nitrogen” factory in Jaworzno, and
then (1924-1927) as a professor’s assistant on chemical
Department of Lviv Polytechnic he taught physical
chemistry, bases of electrochemistry and colloids science.
In 1927 he defended his thesis and became the chairmen
of the Department. In 1928 he was given professor
extraordinary title followed by professor ordinary in 1936.
Prof. T. Kuczynski is the author of about 50 works
and patents. One of his major works is separation of
emulsions by phenol addition, owing to which prof.
Kuczynski became an international expert in the industry.
His another important work is extraction of lubricating
oils by aromatic hydrocarbons derivative. He was also an
adviser of the exploitation of potassium salts Society in
Kalush. Together with the colleagues he conducted the
researches which were widely used in potassium
production, including the new technologies of potassium
salts, research of the multicomponent salt systems, works
with corrosion of materials for equipment production.
Prof. T. Kuczynski was a founder of the Union of
Engineers-Chemists of Poland, as well as one of the
creators and editor-in-chief of “Chemical Review” up to
1939. He developed chemical engineering – a new direction
in Polish science and industry. For these purposes he used
III
part of the laboratories of the Department he chaired. His
lectures on chemical technology of basic inorganic
synthesis and metallurgy consisted of two parts.
The first part meant for the third year students was
devoted to the chemical engineering and contained such
sections as history of development of chemical technology
and chemical industry; theory of chemical processes; raw
materials; equipment; technological regimens; optimum
parameters; choice of materials for chemical equipment;
technological schemes; division and cleaning of gases;
dissolution, evaporation under pressure, crystallization,
drying, etc.
The second part for the fourth year students included
obtaining of gases (hydrogen, nitrogen); production of
fertilizers; synthesis of ammonia, nitric acid and other
nitrogen compounds; obtaining phosphorus, phosphoric
acid, and superphosphate; potassium and mixed fertilizers;
hydrochloric and sulfuric acid; soda. Metallurgy; theory
of corrosion and anticorrosion protection; special alloys;
electrolysis were also lectured.
In addition, for the fourth year students prof.
Kuczynski lectured technical electrochemistry including:
accumulators; bases of electrolysis; electrolysis of water,
chlorides, electrolysis under pressure; electro-osmose, etc.
After annexation of Lviv to soviet Ukraine in 1939 Lviv
Polytechnic was renamed to Lviv polytechnic institute and
the Department to Department of inorganic technology.
At that time (1939-1941) professor Kuczynski was
lecturing only chemical engineering. During the German
occupation in 1941-1944 higher educational institutes in
Lviv were liquidated, and a few months later Technical
Professional Courses in Lviv Polytechnic were organized.
Prof. T. Kuczynski taught there inorganic technology and
took part in the clandestine teaching of the students. Before
escape from Lviv the Germans robbed Lviv Polytechnic
and the Department in particular taking away the apparatus
and equipment. After their escape prof. Kuczynski initiated
the renewal of the Department and headed it till January 3,
1945, when he was arrested together with his colleagues
from Lviv Polytechic by National Commissariat of Internal
Affairs (NCIA). He was put to prison, than to the camp in
Krasnodon. After being released he was taken to
Voroshilovgrad where he died in a hospital on June 25,
1945.
Appearance and quick growth of the technology of
inorganic substances in Lviv Polytechnic were caused by
the fact that in the end of the 19th and in the beginning of
20th century the mineral resources of Carpathian-region
(primarily polymineral potassium ores) began to be widely
used in the industrial production.
From 1945 to 1960 the head of the Department
was associate professor Andriy Zhyvotovsky and the
Department was named „Technology of inorganic
substances”. At that time merely 20-25 specialists in
inorganic technology were being trained. „General chemical
 Tamara Perekupko et al.
technology” course was read for the chemistry students
of Lviv polytechnic institute. In spite of the fact that our
Department was the first in Ukraine to start teaching
technical electrochemistry in 1912, for some unknown
reasons training of electrochemists was not renewed
although there was an acute shortage of such kind of
specialists in our region at that time. The second Department
of technical electrochemistry was created in Kyiv
polytechnic institute in 1929 followed by Kharkiv
polytechnic institute in 1930 and Dnipropetrovsk chemical-
ingineering institute in 1953. Absence of training of
specialists of technical electrochemistry in a post-war
period in the Western region of Ukraine brought
considerable harm to the technical level of the industry of
this region.
We have all grounds to state that the absence of
training of specialists in electrochemists was due to the
absence of qualified instructors in this field murdered in
the period of 1939-1945. Scientific research work of the
Department was focused on the improvement of
production of nitrate and sulfate acid, technology of
thermophosphates, creation of more efficient mass
exchange equipment, in particular an absorber with
S-similar dispersers. It is necessary to notice that the period
of A. Zhyvotovsky chairmanship was a post-war and hard
for the economy of the former USSR. As a result the
Departments were underfunded and laboratory-technical
base was poor. It had the negative influence on the intensity
of scientific research works and on the level of the
specialists training.
The end of the 50th of the 20th century was
characterized by a decline in the chemical industry in the
USSR, the admission of the students-chemists was
reduced, Departments were closed (merged), etc. In
particular, in 1956 the greater part of the students-chemists
of Lviv Polytechnic was moved to the new speciality –
“Controlling and measuring apparatus”. In 1960 the
Department of technology of inorganic substances was
merged with the Department of processes and apparatus
of chemical productions under the direction of associate
professor Alexander Chernyavsky. It was a tough period
in the history of our Department. Such amalgamation was
artificial and it inflicted considerable harm to the
development of the two Departments, as they both had
different specifics of educational process and orientation
of the scientific work.
At that time in Western Ukraine chemical inorganic
industry was developing rapidly. It was caused by the
powerful sources of raw materials of the region. In 1959
mining-chemical industrial complex in Rozdil output the
first product (sulfur), chemical metallurgical complex in
Kalusch, mining-chemical complex in Yavoriv, potassium
factory in Stebnyk, a complex of nitrogenous fertilizers in
R³vno, etc. were developing. There was a considerable
disbalance between the number of specialists of inorganic
IV
technology required by the industry and the number of the
specialists graduating from Lviv polytechnic institute. This
deficit was compensated by the graduates of other higher
educational institutions of the USSR. As a rule, they failed
to get acclimatized here. The situation became even more
complicated when in 1968 admission of students was
stopped on speciality “Technology of inorganic
substances”. This was explained by the absence of
scientific-teaching staff of the proper level and a separate
Department.
Victor Yavorsky, a young scientist (born 1937) and
graduate of the Department of technology of inorganic
substances of Lviv polytechnic institute, being aware of
the importance of training of specialists in this speciality,
made a lot efforts to restore the independence of our
Department. In 1969 the incorporated Department was
parted to the two separate Departments: chemical
technology and processes and apparatus of chemical
productions. This became possible owing to support of
the Dean of chemical-technological Faculty professor
Vasiliy Tikhonov and the Rector of the Institute professor
Grigory Denysenko. In 1971 stationary form of study was
halted, but training of students of external form began (two
groups). Associate professor V. Yavorsky became the head
of the Department of chemical technology. Its laboratory-
technical base was of low level, research work was
conducted only by the teachers individually and financed
from the state budget.
At the same time inorganic industry, which was
actively developing in the Western regions of Ukraine needed
rapid solutions for a great number of scientific and
engineering problems. The raw materials base for sulfuric
industrial complexes in Rozdil and in Yavoriv were the natural
sulfuric ores of the Carpathian region. Implementation of
the large complex of research works was needed to organize
an effective process of extraction of sulfur from sulfuric
ore, increasing its quality, decreasing the production volumes,
expanding the range of the commodities and special types
of the finished products, etc. At that time the sulfuric industry
of USSR had practically no proper scientific base. A small
laboratory of sulfur in the State institute of mining-chemical
raw materials (Lyubertsi in Moscow region) with the staff
of 8 persons could not provide the solutions to the vital
scientific questions appeared in the process of the sulfuric
industry development.
The above mentioned was also true for polymineral
potassium ores of the Carpathian region as the unique
source of potassium substances in Ukraine. Therefore there
was an acute need for the scientific personnel of higher
qualification which could define and solve complex
problems of theory and practice of sulfur and potassium
salts technologies.
Starting from 1969 under the direction of professor
V. Yavorsky a wide range of research works devoted to
the solution of the major problems of sulfur and potassium
 Department of Chemistry and Technology of Inorganic Substances: the Past, the Present, the Future
technologies were launched. In short time a considerable
volume of scientific researches devoted to the elimination
of the defects of the existing technologies, their
improvement and intensification, the development of the
novel technologies of obtaining end products from the new
powerful sources of raw materials was conducted by the
staff of the Department, the postgraduate students, and
the seekers. Considerable attention was given to increase
of quality of the obtained products as well as to harmful
waste neutralization and utilization. The researches were
conducted in close collaboration with the sulfuric and
potassium plants.
With the money obtained from the research works
conducted for the industrial plants scientific laboratories
were modernized and equipped by the newest apparatus.
This allowed to raise the level of the educational process
and the scientific-research works as well as successfully
train scientific and scientific-pedagogical personnel of
higher qualification. Annually 2-3 postgraduate students
or co-seekers defended their thesis on the Department.
This enabled to properly staff the Department with
scientific-pedagogical personnel as well as supply sulfuric
and potassium industries with the qualified researchers. It
was mainly the research workers, trained on the
Department, who organized the Central research laboratory
of sulfur in New Rozdil and worked in Kalush branch of
the all-USSR Research Institute of halurgy.
In 1973 the Department of chemical technology
was appropriated such fundamental course of chemical
training of chemists-technologists as “General and
inorganic chemistry”. In 1990 it was renamed to the
Department of chemistry and technologies of inorganic
substances. Integrating the courses of theoretical inorganic
chemistry with inorganic technology appeared very fruitful,
as it enabled to increase the scientific level of the special
courses teaching and to teach theoretical courses more
target oriented. In 1989 admission of the students of
stationary form of teaching was renewed on speciality
„Technology inorganic substances”, and in 1992 on
speciality “Technical electrochemistry”.
Under the direction of professor V. Yavorsky the
first scientific school of the problems of chemistry and
technology of sulfur and its major combinations in Ukraine
was created on the Department. Its great achievements
were the new technological developments, major part of
which was applied in the industry. These are the following:
– cleaning of natural sulfur from flying organic
admixtures by air (Rozdil Production Association “Sulfur”,
in 1970);
– cleaning of natural sulfur from organic admixtures
by the overheated aquatic steam and sulfate acid (Rozdil
Production Association “Sulfur”, in 1982);
– cleaning of oxygen containing gases from
hydrogen sulfide using the quinhydron method (Rozdil
Production Association “Sulfur”, in 1983);
V
– the complex of research works on improvement
and intensification of the sulfur production processes form
different types of raw materials (Rozdil and Yavoriv
Production Association “Sulfur”);
– cleaning of the sulfate-acid systems gases emission
(JSC “Crimean titanium”, 2004);
– cleaning of volley emissions of ilmenite sulfate-
acid decomposition reactors (JSC “Crimean titanium”, in
2005);
– utilization of warmth and cleaning of emissive
gases of methatitanic acid paste calcinators (JSC “Crimean
titanium”, in 2005);
– cleaning of smoke gases of colored iron oxide
production (JSC “Crimean titanium”, in 2006).
Great scientific achievements of the Department
were also made in the technology of potassium and
phosphoric fertilizers. A range of new ecologically clean
technologies of the complex processing of domestic
polymineral potassium ores of the Carpathian-region was
developed. Scientific-technological bases of solid-phase
reducing of phosphates and sulfates by natural gas in the
presence different additives were elaborated. Topicality and
value of these works is growing in connection with the
acute need for utilizing the domestic phosphatic ores in
the industrial production, as up to now our phosphoric
fertilizers industry has been working on imported raw
material. A new direction in the technology of phosphoric
fertilizers is being developed – transforming water insoluble
phosphorus forms to water soluble ones by thermal
processing of domestic phosphorites with additives. For
the last 15 years the researches directed at utilization of
the nonferrous, rare and precious metals from various
wastes of production, dead catalysts, etc have been started.
Based on the results of the researches a monograph
“Technologiya sery” and over 700 scientific works were
published. The novelty of these scientific works was
proved by over 140 inventions considerable part of which
was applied in the industry. During the last 35 years 47
candidate’s and 5 doctoral dissertations have been
defended.
The academic subjects taught at the Department
are fully provided by the methodical materials which are
being systematically renewed. Considerable attention is
given to writing textbooks and other educational materials.
For instance, textbook “General chemical technology”
(published in 2005) is the only one in Ukraine and has
been awarded the diploma of the 2nd degree in the
nomination “The Best textbook in natural sciences” on the
1st International forum “Informational support of
educational process in High schools”.
Today the Department has a modern laboratory-
technical base and provides training of bachelors, engineers,
and master’s degree students in specialities “Chemical
technology of inorganic substances” and “Technical
electrochemistry”, candidates and doctors of sciences.
Theoretical and technological academic subjects are
organically connected. Thus theoretical disciplines are
taught meeting the requirements of the modern technologies
and the theoretical teaching of technological disciplines is
improved. Since water treatment has been read on the
Department for a long time already, and since the
Department is staffed with the instructors of the necessary
qualification and equipped with material and methodological
resources starting from the next year a new speciality
“Technology of drinking water and water processing for
food productions” is planned to be launched. It is common
knowledge that the quality of most food products is
determined by their base which is usually water.
Consequently such specialists are highly demanded by the
modern food industry.
The highly qualified scientific personnel of the
Department consists of 4 doctors, 14 candidates of
sciences and is mainly staffed by the graduates of the
Department, its former postgraduate students doctoral
candidates, is capable of solving complex pedagogical and
scientific and technical problems faced higher school and
industry of Ukraine.
In 2007 on the occasion of 70th birthday of the
head of our Department, the Honoured Science and
Technology Worker of Ukraine, academician of
Engineering Academy of Sciences of Ukraine, Ecological
Academy of Sciences of Ukraine, New York Academy of
Sciences, professor, doctor of engineering sciences Victor
Yavorsky and his outstanding achievements in science,
fruitful pedagogical activity and training of scientific-
pedagogical personnel of high qualification he was entitled
Honoured Professor of National University Lviv Polytechnic
National University. Only two heads of the same
Department were entitled such a high rank: I.Moscicki
and V. Yavorsky. Number 7 is really lucky for our
Department: I. Moscicki was the seventh Honoured
VI
professor of Lviv Polytechnic, 81 years later V. Yavorsky
was entitled the 21st Honoured Professor. During these
years not only our Department preserved the glorious
initiatives of its first leaders, but managed to increase and
develope the creative and pedagogical traditions.
The collaborators of our Department take pride in
the prominent scientists G. Gyunzberg, B. Pavlevski,
I. Moscicki, T. Kuchinski, A. Zhivotovskiy V. Yavorsky
and others who made a great contribution to the
establishment and development of our Department and
expresses hope that the Department’s glorious history and
traditions will be cherished and developed by the coming
generations.
References
[1] Stanik W.:Ch&ChT, 2007, 1, XI.
[2] Zajaczkowski W.: C.K. Szkola Politechniczna we Lwowie.
Rys historyczny jej zalozenia i rozwoju, tudziez stan jej obecny.
Lwow 1894.
[3] Politechnika Lwowska 1844-1945. Wroclaw 1993.
ÊÀÔÅÄÐÀ ղ̲¯ ² ÒÅÕÍÎËÎò¯
ÍÅÎÐÃÀͲ×ÍÈÕ ÐÅ×ÎÂÈÍ:
ÌÈÍÓËÅ, ÑÜÎÃÎÄÅÍÍß ² ÌÀÉÁÓÒͪ
Àíîòàö³ÿ. Ç íàãîäè 140-ð³÷÷ÿ â³ä äíÿ íàðîäæåííÿ
ïðîôåñîðà, äîêòîðà hînoris causa ³ Ïî÷åñíîãî ïðîôåñîðà
Ëüâ³âñüêî¿ ïîë³òåõí³êè, êîëèøíüîãî çàâ³äóâà÷à êàôåäðè
². Ìîñöèöüêîãî ³ 70-õ ðîêîâèí ïðîôåñîðà, äîêòîðà òåõí³÷íèõ
íàóê, Ïî÷åñíîãî ïðîôåñîðà Ëüâ³âñüêî¿ ïîë³òåõí³êè, íèí³øíüîãî
çàâ³äóâà÷à êàôåäðè Â. ßâîðñüêîãî, çðîáëåíî êîðîòêèé åêñêóðñ
â ³ñòîð³þ êàôåäðè õ³ì³¿ ³ òåõíîëî㳿 íåîðãàí³÷íèõ ðå÷îâèí
«Ëüâ³âñüêî¿ ïîë³òåõí³êè», ðîçãëÿíóòî ¿¿ ñüîãîäåííÿ ³
ïåðñïåêòèâè.
Êëþ÷îâ³ ñëîâà: icòîð³ÿ, êàôåäðà, òåõíîëîã³ÿ
íåîðãàí³÷íèõ ðå÷îâèí, òåõí³÷íà åëåêòðîõ³ì³ÿ.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No 1, 2008
J. Pielichowski1, R. Kozlowski2, G. Zaikov3 and L.Madyuskina3
IXTH INTERNATIONAL CONFERENCE ON FRONTIERS
OF POLYMERS AND ADVANCED MATERIALS
1
T. Kosciusko Cracow University of Technology, 24 Warszawska str., 31-155, Cracow, Poland
2
Institute of Natural Fibers, 71B Wojska Polskigo str., 60-630 Poznan, Poland
3
N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences
4 Kosygin str., Moscow 119334, Russia, chembio@sky.chph.ras.ru
The IXth International Conference on Frontiers of
Polymers and Advanced Materials was held in Cracow
(Poland) in the period of July 8-12, 2007. The first
conference was held in Delhi, India, January 20-25, 1991
and was inaugurated by the Prime Minister of India. The
second conference was held in Jakarta, Indonesia, January
10-15, 1993, was inaugurated by President Soeharto in the
Presidential Palace, and numbered 244 participants from 24
countries. The third conference was held in Kuala Lumpur,
Malaysia, January 16-20, 1995 and was scheduled to be
inaugurated by the Prime Minister. The fourth conference
was held in Cairo, Egypt, January 4-9, 1997 with the Minister
of Scientific Research of the Government of Egypt as the
Honorary Chair. Three hundred and fifty participants from
30 countries covering all continents participated in the
conference. The fifth conference was held in Poznan,
Poland, June 21-25, 1999, with the Minister-Chairman of
State Committee for Scientific Research, the Minister of
Education, and the Minister of Economy as Honorary
Chairpersons. The sixth conference was held in Recife
(Pernambuco, Brazil), May 4-9, 2001 with Minister of
Science and Technology of Brazil and Rector of the Federal
University of Pernambuco as Honorary Chairpersons. The
conference was attended by about 250 participants from
25 countries. The seventh ICFPAM was organized by
University POLITEHNICA of Bucharest, in Bucharest,
Romania, June 10-15, 2003. President of Romania, Minister
of Education and Research, Minister of Industry and
Resources were Honorary Chairpersons of the conference.
The conference numbered about 300 participants from more
than 30 countries. The last conference (VIIIth) was
organized by University of Mexico in Cancun (Mexico,
Quintana Roo), April 22-29, 2005.
The conference provides a unique blend of science,
technology and business. It brings together leading
international scientists, engineers, top-level industrial
management, and business executives for discussions on
the status of advanced materials, new technologies and
industrial and business opportunities.
The main objectives of the conference are:
· To highlight advances and new findings in polymers
and advanced materials and their impact on new
technologies
VII
Current Events
· To facilitate technology transfer and new business
opportunities by bringing together representatives from
academia, research centers, industries, and business
· To foster international collaborations and joint
ventures
· To facilitate the growth of private sector business
in Eastern Europe and Poland in particular
· To promote the growth of scientific and technical
infrastructure in the field of polymers and advanced
materials technologies.
Prof. M. Sewerynski (Minister of Science and
Higher Education, Poland), Mr. P. G. Wozniak (Minister of
Economy), Prof. J. Majchrowski (Mayor of the City of
Cracow), Prof. J. Gawlik (Rector of the Cracow University
of Technology, Poland), Prof. M. Kleiberg (President of
Polish Academy of Science, Poland) and Dr. Eng. W.
Ratynski (President of Polish Federation of Engineering
Associations (FSNT-NOT), Poland) have been honorary
chairpersons of the IXth Conference in Cracow.
Prof. P. N. Prasad (Executive Director, The Institute
for Lasers, Photonics and Biophotonics Buffalo, NY, USA)
has been an Honorary International Chairperson. Dr. Francois
Kajzar (Research Director, CEA-DRT/LITEN DSEN/L2C,
CE Saclay, France) has been an International Chairperson.
Prof. Ryszard Kozlowski (Director of Institute of Natural
Fibers, Poznan, Poland) and Prof. Jan Pielichowski (Director
of Polymer Science Department, Cracow University of
Technology, Poland) have been National Chairpersons. Prof.
A. Ikushima (Toyota Technological Institute, Nagoya,
Japan), Prof. K. S. Lee (Hannam University, Taejon, South
Korea) and Prof. J. E. Mark (Distinguished Res. Prof.
Department of Chemistry, University of Cincinnati, OH, USA)
have been Co-Chairpersons. Dr. J. Grote (Senior Electronics
Engineer Air Force Research Laboratory Materials and
Manufacturing Technology Directorate, Dayton, USA) has
been an International Coordinator and Dr. F. Charra (CEA-
DSM, CEA Saclay, France) has been International Secretary.
International Advisory Committee has included
world-known scientists from several countries: Prof.
A. Meghea (University POLITEHNICA of Bucharest,
Romania), Dr. Ch. Andraud (ENS, Lyon, France),
 J. Pielichowski et al.
Dr. D. Chrisey (Center for Nanoscale Science and
Engineering, NDSU, Fargo,USA), Prof. R. Delobel
(CREPIM, France), Prof. J. C. Dubois (Nemoptic,
Guyancourt, France), Prof. Z.J. Florianczyk (Warsaw
University of Technology, Poland), Prof. A. Graja (Institute
of Macromolecular Physics Poznan , Poland), Prof.
J. Jamrozik (Jagiellonian University, Cracow, Poland),
Prof. F. E. Karasz (University of Massachusetts, Amherst,
MA, USA), Prof. A. Leao (UNESP-Universidade Estadual
Paulista,Botucatu, Brazil), Dr. C. Y. C. Lee (US Air Force
Office for Scientific Research, USA), Prof. S. Lefrant
(Nantes University, France), Prof. H. Sasabe (Chitose
Institute of Science and Technology, Japan), Prof.
L. Slusarski (Technical University of Lodz, Poland), Prof.
J. Sworakowski (Wroclaw University of Technology,
Poland), Prof. J. Ulanski (Lodz University of Technology,
Poland), Dr. D. J. Williams (KODAK, USA) and Prof.
G. E. Zaikov (Russian Academy of Sciences, Russia).
The conference has included general plenary talks,
tutorials, invited lectures, contributed talks as well as poster
sessions. An exhibition on polymers, advanced materials,
equipment, and recent applications has also been organised
within the conference.
The program of the Conference included 8 sessions:
1. General and tutorial lectures on New Materials
and Advanced Technologies.
Lectures covering the main conference topics and
emphasizing their impact on educational, scientific,
technological and business trends.
Symposium Chairs: Prof. K. S. Lee (Hannam
University, Korea) and Prof. M. S. Kolwas (Institute of
Physics, PAN, Warsaw, Poland).
2. New Generation Nanostructured Materials,
Hybrid Materials, Glass and Ceramic, Dental Materials,
Exotic Materials.
Lectures presenting new areas of application and
latest results in research and development.
Symposium Chairs: Prof. J. Mark (University of
Cincinnati, OH, USA) and Prof. K. Haberko (AGH
University of Science and Technology, Cracow,Poland).
3. Natural Fibres, Composites and Environmentally
Friendly Materials.
Natural fibres and composites based on cellulosic
fibres, natural textiles, agro-fine chemicals; applications
in pulp and paper industry, biodegradable materials.
Symposium Chairs: Prof. R.Kozlowski (Institute of
Natural Fibres, Poznan, Poland) and Prof. R. M. Rowell
(USDA Forest Service, Madison, WI, USA)
4. Polymeric Materials and Composites for Plastic
Electronics and Solar Energy Conversion. Conducting
polymers, field effect transistors, light emitting devices;
organic light detectors, polymer lasers; organic solar cells.
Symposium Chairs: Prof. A. Pron (CEA Grenoble,
France) and Prof. M. Zagorska (Warsaw University of
Technology, Warsaw, Poland).
VIII
5.Advanced Materials and Composites for
Photonics, Nano- and Biophotonics.
Photorefractive polymers, nonlinear optical
materials; materials for image and information processing,
optical storage; polymer light amplifiers; liquid crystals and
liquid crystalline polymers; materials for integrated optics.
Symposium Chairs: Prof. I. C. Khoo (The
Pennsylvania State University,University Park, USA) and
Prof. A. Miniewicz (Wroclaw University of Technology,
Wroclaw, Poland)
6. Biomaterials and Biotechnology.
Polymers and composites as implant in body for
structural members and as replacements of flexible tissue
in reconstructive surgery, bioimaging, nanomedicine drug
delivery, bioMEMS, biofilms, tissue engineering.
Symposium Chairs: Dr. G. Bidan (CEA Grenoble,
France) and Dr. D. Crisey (North Dakota State University
Fargo, ND, USA).
7&8. New Polymers in Ecology & Thermal
Degradation, Stabilization and Flame Retardancy of
Polymeric Materials.
Synthesis and application of polymers for environ-
mental protection. Environmentally – Safe technologies for
sustainable developments in polymer technology.
Thermal- and photo-degradation, stabilization and
flame retardancy of polymeric materials -
(co)polymers, blends, natural polymers, (nano)composites.
Fundamentals and applications.
Symposium Chairs: Prof. K. Pielichowski (Cracow
University of Technology, Krakow, Poland) and Prof. S.
Bourbigot (Ecole Nationale Supérieure de Chimie de Lille,
France).
Keynote speakers of the Conference:
- Prof. J. I. Jin (Korea University, Seoul, Korea)
“Polymers with unique properties”.
- Dr. K. Blakely (NanoDynamics, Inc, Buffalo, USA)
“Disruptive Approaches to the Global Energy Situation:
The Power of Nanotechnology”.
- Prof. Y. Koike (Keio University, Japan) “Status of
Photonics Polymers for “Fiber to the Display”.
- Prof. R. Kozlowski (Institute of Natural Fibers,
Poznan, Poland) “Latest achievements in the area of
composites reinforced with natural fibers”.
- Prof. K. Matyjaszewski (Carnegie Mellon
University, USA) “Nanostructured functional materials via
ATRP with ppm amounts copper”
- Prof. P. N. Prasad (Executive Director, Institute
for Lasers, Photonics and Biophotonics Buffalo University,
USA) “Opportunities for Multifunctional Nanomaterials in
Biotechnology and Nanomedicine”.
- Prof. N. S. Sariciftci (Johannes Kepler University
of Linz, Austria) “Organic Optoelectronic Devices”.
- Prof. J. Zyss ( ENS Cachan, France) “Revivals
of molecular nonlinear optics from the micro to the
Nanoscale”.
 IXth International Conference on Frontiers of Polymers and Advanced Materials
The main organizers of the conference have been
Tadeusz Kosciuszko Cracow University of Technology
(Cracow, Poland) and Institute of Natural Fibers (Poznan,
Poland).
Conference sponsors:
Cracow University of Technology
Institute of Natural Fibers
International Union for Pure and Applied Chemistry
European Office of Aerospace Research and
Development (London)
Office of Naval Research Global (London)
Toyota Motor Company (Japan)
Samsung Corp. (Korea)
Taylors & Francis Group (USA)
Two workshops have been organized within the
Conference: “Contribution of FP 6 ToK-Nanotec-est project
to enhance European mobility and researcher career
opportunities offered by new FP 7 programme” (Chair
A. Meghea) and “Molecular nano- and biophotonics for
telecommunication and biotechnology” (Chair
A. Miniewicz).
About 400 scientists, students and engineers from
85 Universities research centers from 44 countries (Poland,
France, USA, Romania, Japan, Italy, Irland, South Korea,
Ukraine, Russia, Germany, China, Singapore, Mexico,
Australia, Israel, Brazil, Chile, Iran, Turkey, Malaysia,
Belgium, Switzerland, Portugal, Sweden, Indonesia, New
IX
Zealand, Argentina, India, Canada, Norway, UK, Lithuania,
Latvia, Hungary, Finland, Spain, Check Republic, The
Netherlands, Morocco, Slovenia, Bulgaria, Slovakia and
Algeria) have taken part in this conference.
About 200 oral reports have been presented in 8
sessions and two poster sessions have included 160
presentations. The conference has been actively attended
by young scientists (PhDs. students, assistants, and post-
docs), who have presented a number of interesting oral
talks and posters.
The conference has showed that investigation of
properties and applications of new polymeric and composite
materials with new unique properties is very important
from the point of view of pure and applied chemistry. A
special attention should be paid to degradation and
recycling of plastics after their life-time expiration.
The proceedings of the conference can be found in
the libraries of Cracow University of Technology (Cracow),
Institute of Natural Fibers (Poznan) and N.N. Semenov
Institute of Chemical Physics, Russian Academy of
Sciences (Moscow). They have also been handed over to
the participants of the conference.
Two countries are bidding to host the next
Xth International Conference in 2009. These are Morocco
and Chile. The final decision regarding the place and the
exact date of the next conference will be taken by the
Scientific Committee by the end of the year 2007.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No 1, 2008
Gennady Zaikov and Marina Artsis
XXXI INTERNATIONAL VACUUM MICROBALANCE
TECHNIQUES CONFERENCE
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences
4, Kosygin str.,Moscow 119334, Russia, chembio@sky.chph.ras.ru
XXXI International vacuum microbalance
techniques conference was held in Izmir (Turkey) in the
period of September 12-14, 2007. The conference has
been organized by Izmir Institute of Technology (Faculty
of Engineering, Department of Chemical Engineering,
Culbance Koyu-Urla-Izmir,Turkey).
About 100 scientists from 45 research centers of
universities, academic institutes and companies representing
11 countries (Turkey, Germany, Poland, Ukraine, Russia,
Finland, UK, China, The Netherlands, Bulgaria, and USA)
including Profs. Zulfiqur Ali (University of Teesside,
Middlesbrough, UK), Devrim Balkose (Izmir Institute of
Technology, Izmir, Turkey), Hassan Barkia (Ecole Normale
Superieure, Rabat, Morocco), Labri Belkbir (Universite
Mohommaed V, Rabat Morocco), M’barek Ben Chanaa
(Universite Cadi Ayyad, Marrakesh, Morocco), Grzegorz
W. Chadzynski (University of Technology. Wroclaw,
Poland), Th. Cast (Technische Universitat Berlin, Germany),
S. Amarasiri A. Jayaweerea (School of Science and
Technology, University of Teeside, Middlesbrough. TSI BA,
UK), Mohamed Jemal (Universite de Tunis, Tunisia), Jurgen
U. Keller (Universitat Siegen, Siegen, Germany), Carel
H. Massen (Technische Universiteit, Eindhoven,
Netherlands), Johannes A. Poulis (Technische Universiteit,
Eindhoven, Netherlands), Erich Robens (Johannes
Gutenberg-Universitat, Mainz, Germany), Piotr Staszczuk
(Universytet Maria Curie-Sklodowska, Lubin, PL), Valentin
A. Tertykh (Ukrainian Academy of Science of Ukraine, Kiev,
Ukraine) have taken part in the conference.
Prof. Devrim Balkose (Izmir Institute of
Technology), Prof. Erich Robens (Institute of Inorganic
and Analytical Chemistry, Jonnaes Gutenberg University,
Mainz, Germany) and Prof. Semera Ulim (former director
of Izmir Institute of Technology) have taken part in the
opening ceremony of this conference.
The program of the conference has included 8 oral
sessions and 2 poster sessions. Prof. Gennady E. Zaikov
(Institute of Biochemical Physics, Moscow, Russia) and
Prof. Gurel Nisli (Ege University, Izmir) have chaired the
first session. Two lectures have been included in this
session. Prof. E. Robens (co-author dr. S. Kiefer from
Philipp-Matthaus-Hahn Museum, Kasten, Germany) have
presented information about some intriguing items in the
history of scientific balances. Report of G. W. Chadzynski
XI
Current Events
(Institute of Physics, Faculty of Fundamental Problems
of Technology, Wroclaw University, Wroclaw, Poland) co-
authored by P. Staszczuk, D. Sternik, and M. Blachnio
(Department of Physicochemistry of Solid Surface,
Chemical Faculty, Maria Curie-Sklodowska University,
Lubin, Poland) was on studies of physico-chemical
properties and fractal dimensions of selected high-
temperature superconductor surfaces.
Prof. P. Staszczuk (School of Science and
Technology, University of Teeside, Middlesbrough, UK)
and Prof. Semra Ulku (Izmir Institute of Technology) have
been the chairpersons of second session. Three lectures
have been included in this session.
Prof. Valentin A. Tertykh (Institute of Surface
Chemistry of National Academy of Sciences of Ukraine,
Kyiv, Ukraine) has spoken about silica adsorbents with
chemical specificity of surface and desired geometrical
characteristics. A report by Y. Erten, A. Gunes Yerkesilikli,
A. E. Cetin and F. Cakicioglu Ozkan (Izmir Institute of
Technology, Department of Chemical Engineering Urla,
Izmir) has covered CO 2 adsorption and dehydration
behavior of LiNaX, KNaX, CaNaX and CeNaX zeolites.
The last report in this session has been presented by a
group of authors (D. Yalcin, O. Ozcalik, E. Altiok and
O. Bayraktar, Biochemical Engineering Research
Laboratory, Department of Chemical Engineering, Izmir
Institute of Technology). The contributors have shared
information about characterization and recovery of tartaric
acid from wastes of wine and grape juice industries.
The third session has been chaired by Prof. Devrim
Balcose and Prof. Mehmet Polat (Izmir Institute of
Technology). There have been two lectures in this session.
Investigations of adsorption and porosity properties
of carbon-covered alumina surfaces have been discussed
in the lecture of P. Staszczuk, M. Bachnio (Department of
Physicochemistry of Solid Surface, Chemistry Faculty. Maria
Curie-Sklodowska University, Lublin, Poland) and L. Lin,
Y. X. Zhu (Stae Key Laboratory for Structural Chemistry
of Unstable and Stable Species, College of Chemistry and
Molecular Engineering, Peking University, Beijing, China).
A. Dabrowski, M. Iwan, E. Mendyk, Z. Rzaczynska (Mari
Curie-Sklodowska University, Lublin, Poland) and E. Robens
(Mainz, Germany) have presented data about investigation
of surface properties of lunar regolith.
 Gennady Zaikov et al.
Prof. V. A. Tertykh, Prof. Muchsin Ciftcioglu (Izmir
Institute of Technology) have chaired the 4th session. The
session consisted of 3 lectures.
The design and practical implementation of a
commercial in situ gravimetric analyzer for neutron
diffraction studies have been discussed in a lecture of
G. Duffy, M. G. Roper, M. E. Jakson, A. P. Woodhead,
M. J. Benham (Hiden Isochema Ltd, Warrington, UK),
W. I. F. David, M. Sommariva, R. M. Ibberson (ISIS
Facility, Rutherford Appleton Laboratory, Chilton Didcot,
Oxon, UK) and M. O. Jones, S. R. Johnson, P. P. Edwards
(Inorganic Chrmistry Laboratory, University of Oxford,
Oxford, UK). The date about measurement of diffusivity
of water in polysulfone has been presented in a lecture of
M. O. Arslan and S. Alsoy Altinkaya (Izmir Institute of
Technology). Dr. T. Vitala (KSV Instruments Ltd, Helsinki,
Finland) has given talk about modeling liquid and adsorbed/
deposited layer properties with impedance-base quartz
crystal microbalance.
The fifth session has included three reports. Prof.
G. W. Chadzynski and Prof. Saside Alsoy (Izmir Institute
of Technology) have chaired this session. The
measurement of humidity has been discussed in a report
of E.Robens (Mainz, Germany), D. Balcose (Izmir Institute
of Technology), and K. Rubner (Federal Institute for
Materials Research and Testing, Berlin, Germany).
D. Berkun, D. Balkose, F. Tihminlioglu, S. Alsoy Altinkaya
(Izmir Institute of Technology) have delivered a lecture
on sorption and diffusion of water vapor on edible films.
Dr. Y. Yurekli (co-author S. Alsoy Altinkaya, Izmir Institute
of Technology) has spoken about sorption and diffusion
behaviors of butylacrylate in rubbery methylmethacrylate-
butylacrylate copolymer.
Prof. E. Robens and Prof. Fehime Ozkan have
chaired session 6. There have been two lectures in this
session. Combustion of polyethylene nanocomposites has
been discussed in a lecture of Prof. G. E. Zaikov,
S. M. Lomakin, A. L. Rakhimkulov (Institute of
Biochemical Physics, Moscow, Russia), I. L. Dubnikova,
S. M. Berezina (Institute of Chemical Physics, Moscow,
Russia), R. Kozlowski (Institute of Natural Fibres, Poznan,
Poland) and Gyeong-Man Kim, G. H. Michler (Martin-
Luther University, Halle-Wittenberg, Germany). Information
about DNA-Water vapor interactions has been delivered in
XII
the second lecture of this session by Prof. D. Balkose,
B. Alp and S. Ulku (Izmir Institute of Technology).
The chairpersons of session 7 were Prof.
P. Staszczuk and Acc. Prof. Funda Tihminlioglu. Three
lectures have been included in this session.
Thermochemistry of hexaoxoiodates (VII) has been
discussed in a lecture of S. A. A. Javaweera and
E. D. Fiagome (School of Science and Technology
University of Teeside Middlesbrough, UK). In the second
lecture of this session F. Cakicioglu Ozkan, S. Ulku (Izmir
Institute of Technology) has spoken about diffusion
mechanism of H2O in the zeolitic tuff rich in clinoptilolite.
A lecture of Y. Akdeniz, S. Ulku (Izmir Institute of
Technology) has been on thermal stability of Ag-Exchanged
clinoptiolite rich mineral.
The last 8th session (chairmen Prof. Sevgi Ulutan
and Assoc. Prof. Oguz Bayraktar from Izmir Institute of
Technology) has consisted of two lectures. The Jantti-
related functions describing adsorption of gases-
reconsidered have been discussed in a lecture by
E. Robens, J. K. M. Jansen (Faculty of Mathematics,
Technische Universiteit Eindhoven, The Netherlands),
C. H. Massen, J. A. Poulis (Faculty of Applied Physics,
Technishe Universitiet Eindhoven, The Netherlands). The
last lecture of I. D. Atik, F. Tihminlioglu, B. Ozen has
covered water vapor barrier performance of corn-zein
coated polypropylene packaging films.
The poster session has included 16 reports including
the following: influence of surface irregularities on
adsorption, gravimetric adsorption measurements, interface
interaction of ice and water, properties of Lunar regolith,
carbon nanotubes, heterogeneity of solid surfaces, silica-
polyaniline nanocomposites, thermodegradation and
thermooxidation, mesoporous in silicates, determination
of moisture and pharmaceutical powder, glass transition
behaviour, gravimetric sorption apparatus, paraffin wax
application, composites on the base of polypropylene,
characterization of silk and cure kinetics.
Within the conference instruments companies have
organized an exhibition of vacuum microbalance equipment
and computer applications.
The next 32nd conference will be held in 2009 in
Kazimerz (near Lublin), Poland.
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 2, No 1, 2008 Current Events

Gennady Zaikov and Marina Artsis

FIRST INTERNATIONAL CONFERENCE ON BIODEGRADABLE

POLYMERS AND SUSTAINABLE COMPOSITES
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences
4, Kosygin str., Moscow 119334, Russia
chembio@sky.chph.ras.ru

The First International conference on biodegradable
polymers and sustainable composites was held at Alicante
University (Alicante, Spain) in the period of October 3-5,
2007. The chairperson of the conference was Prof. Alfonso
Jimenez from Alicante University (AU). Jose M. Kenny,
Terni, Italy, Inaki Mondragon, San Sebastian, Spain,
Philippe Dubois, Mons-Hainaut, Belgium, Sigbritt Karisson,
Stockholm, Sweden, Luc Averous, Strasbourg, France,
David Plackett, Roskilde, Denmark, Carmen Mijangos,
Madrid, Spain, Alessandro Gandini, Aveiro, Portugal, Alain
Dufresne, Grenoble, France, Ton Peijs, London, UK,
Kristina Oksman, Trondheim, Norway, Carlos Pascoal
Neto, Aveiro, Portugal, Andrea Pipino, Amaro, Italy, Sabu
Thomas, Calcutta, India, Analia Vazquez, Mar del Plata,
Argentina, G. E. Zaikov, Moscow, Russia have been
members of Scientific Committee.
The conference has been aimed at providing a forum
for researchers and engineers from all over the world to
exchange up-to-date ideas and opinions on current research
and new applications of biodegradable polymers and
biocomposites. The meeting has addressed mainly new
developments in packaging, agriculture, and automotive
applications.
The conference programme has included review
lectures delivered by expert speakers from throughout the
world. An industrial exhibition has encouraged an open
discussion between developers, manufactures, and users
of biodegradable polymers and biocomposites. Current
research work in the field has been presented in the format
of short oral communications and posters within the
programme of the conference.
The programme has included the following topics:
· Biodegradable polymers and blends.
· Biobased composites and nanocomposites.
· Characterization and properties.
· Vegetable oil. Polymer and composites.
· Biodegradation and environmental fate.
· New and emerging markets and applications.
· Regulatory and ecological issues.
The conference has been sponsored by Alicante
University along with 10 companies.
Scientific programme consisted of 40 invited
lectures and oral presentations and 100 posters. About 150
scientists from 45 research centers representing 17
countries (Spain, Portugal, France, Italy, Argentina, Russia,
Germany, Sweden, USA, Australia, Hungary, Romania,
China, Danmark, Austria, Chile, Peru) have taken part in
the conference.
The scientific programme has been divided to 8
sessions for invited lectures and oral presentations. Posters
have been presented in two other sessions.
Prof. Alfonso Jimenes (the chairman of the
conference) has taken part in the opening ceremony.
The first session has included two invited lectures
(IL) and two oral communications (OC). Prof. Luc Averous
Laboratoire d’ingenieria des Polymers pour les Hantes
Technologies, Strasbourg, France) has chaired this session.
Alessandro Gandini (University of Aveiro, Aveiro,
Portugal) has delivered IL-1 about partial or total
oxypropylation as a means to prepare novel composites
and macromonomers from renewable resources. In IL-2
Jose Maria Kenny (University of Perudgia, Terni, Italy)
has shared information about biodegradable matrix
nanocomposites for biomedical applications.
Nanocomposites based on renewable materials has
been the subject of OC1 lecture by Kristina Oksman
(University of Lund, Lund, Sweden); OC2 lecture has been
devoted to polymer nanocomposites reinforced with
polysaccharide nanocrystals (Alain Dufresne, University
of Grenoble, France).
J. M. Kenny and Alfonso Maffezzoli (University of
Lecce, Lecce, Italy) have chaired the second session.
There have been five OC lectures in the programme
of this session. An information about preparation and
characterization of biodegradable plasticized starch-g-
poly(butylene adipate-co-terephtalate)-based nanocompo-
sites in film applications has been presented by J. M. Raquez
(University of Mons-Hainaut, Mons, France) while Celine
Chaleat (University of Queensland, Brisbane, Australia) has
spoken about fracture toughness in plasticized starch/
poly(vinyl alcohol) blends. Nanostructured composites
based on cellulose, effects of structure on mechanical
properties have been discussed in a lecture of Marielle
Henriksson (Royal Institute of Technology, Stockholm,
Sweden). Data about environmentally advantageous mild
oxidative transformation of poly(vinyl-chloride) for

XIII
 Gennady Zaikov et al.
sustainable composites has been presented in a speech of
Bela Ivan (Institute of Chemistry, Hungarian Academy of
Sciences, Budapest, Hungary). The last lecture of this
session about PVC plasticizers from renewable resources
has been presented by Alfonso Maffezzoli.
Alain Dufresne has been a chairman of the third
session. One IL lecture and three OC reports have been
included in this session. Luc Averous has spoken about the
improvement of green plastics: nano- and microbiocom-
posites from renewable resources. Three OC reports have
been devoted to sustainable packaging from starch (Kishan
C. Khemani, Plastic Technology Ltd., Altona, Victoria,
Australia) and poly (p-dioxanone)/clays nanocomposites
prepared by in-situ polymerization of p-dioxanone initiated
by lanthanum isopropoxide (Ke-Ke Yang, Department of
Materials, Sichuman University, Chengdu, China). Xiu-Li
Wang (form the same university) has spoken about properties
of poly (p-dioxanone) based blends.
Alessandro Gandini has been a chairman of the forth
session. There have been 2 IL lectures and three OC reports
in this session.
G. E. Zaikov (Institute of Biochemical Physics,
Moscow, Russia) in IL 4 has spoken about bio-damages
of materials (adhesion of microorganisms on materials
surface). Environmental degradation of biodegradable
polymers and biobased composites have been discussed
in IL5 by Sigbritt Karlsson (KTH Chemical Science and
Engineering, Dept. of Fibre and Polymer Technology,
Stockholm, Sweden).
Information about assessing the biodegradability and
the mechanical performance of a biocomposite based on
thermoplastic starch reinforced with cotton fibre has been
presented in the OC by Rosana Moriana (Valencia
University of Technology, Spain). Two last OC reports of
this session have been devoted to degradation in soil study
of stereocopolymers of poly (lactic acid) by thermal
analysis (L. J. Santonja Blasco, Polytechnic University of
Valencia, Spain) and system of biodegradability evaluation
on leather used in the footwear industry (M. A. De la Casa,
The Technological Institute, Elche, Spain).
The fifth session has been chaired by David Plackett
(Polymer Department, Technical University of Denmark).
Six OC reports have been included in this session.
In the first OC M. J. A. van den Oever (Wageningen
UR Biobased Products, Wageningen, The Netherlands) has
reported about natural fibre-PLA composites (processing
and mechanical properties). In the second OC R. Forstner
(Transfercenter for Polymer Technology, Upper Austrian
Research GmbH, Wels, Austria) has given information about
the influence of natural rubber content processing
parameters on degradable PLA composites with high impact
strength. The next four OC reports have covered the
following topics: copolymers from lactic acid, e-
caprolactone, poly(ethylene oxide) and toluene diisocyanate
(Novel biodegradable thermoplastics) (Sandor Keki,
XIV
University of Debrecen, Debrecen, Hungary), new multistar
sensor- DSC goes submicrowatts (Francesc Catala, Mettler
Toledo Co., Spain), correlation between poly(vinyl
alchohol) cryogel swelling capacity and synthesis
parameters (Silvia F. C. Patachia, “Transilvania” University
of Brasov, Department of Chemistry, Romania), and
Biodegradable composite films for food packaging
(I. M. Coelhoso, University of Lisbon, Portugal).
Gennady E. Zaikov has been a chairman of the six
session. Five OC reports have been presented in this
session.
In the first OC Jonas Enebro (Fire and Polymer
Technology, School of Chemical Science and Engineering,
Royal Institute of Technology, Stockholm, Sweden) has
spoken about investigation of endoglucanase selectivity
towards carboxymethyl cellulose. Effects of a maleated
polypropylene coupling agent onto the rheological properties
of cellulose-reinforced polypropylene composites have been
discussed in a presentation by Carlos Gonzalez Sanchez
(University of Oviedo, Oviedo, Spain). The third OC has
been delivered by Zoubida Pilato(University of Le Mone,
France) and had title “Chemical characterization of by-
products degradation of polymers by fungal action”. Analia
Vazquez (Institute of Material Science and Technology,
University of Mar del Plata, Argentina) in the fourth OC
has spoken about recent results in biodegradable composites
based on natural fibres. The last OC has been on
biodegradable films from a galactose-rich polysaccharide
produced by a pseudomonas strain from glycerol
(V. D. Alvez, University of Lisbon, Portugal).
Session seven has been chaired by J. M. Kenny.
The session has included 1IL and 4 OC presentations. In
his IL David Plackett has spoken about developments in
biopolymer nanocomposites for food packaging
applications. Inaki Mondragon (Polytechnical School,
Bielao, Spain) in the first OC of this session has presented
data about lignins and tannins as substitutives for phenol
in novolac resins. Autohydrolysis of lignocellulosic
substrates as a strategy for producing green composites
has been discussed in OC of Juan Carlos Parajo (University
of Vigo, Vigo, Spain). Data about boidegradable and
biomass based plastics as the plastics of Europe perspective
has been presented in the OC of Juan Ruiz ( Plastics Europe
Perspective Association, Madrid, Spain), and the last OC
of this session has been on laccase mediated lignin
degradation in the bleaching of Eucaliptus Globulus kraft
pulp (J. C. Villar, Center of Investigation of Biogas, Sant
Yago, Chile).
Sigbritt Karlsson has been the chairperson of the
last 8th oral session. There have been six OC reports in
this session.
Andreia F. de Sousa (The Chemical Faculty,
University of Aveiro, Portugal) has shared information about
novel biopolyesters from suberin monomers. Development
and characterization of novel nanobiocomposites of
 First International Conference on Biodegradable Polymers and Sustainable Composites
thermoplastic biopolymers and layered silicates have been
discussed in the OC of M.D. Sanchez-Garcia (Institute of
Agrochemistry and Food Industry, Valencia, Spain). Cristian
J. Grande (Catholic University in Peru, Lima, Peru) has
spoken about characterization of the collagenhydroxyapatite
nanocomposite laminate structure of fish scales from
arapaima gigas. The last three OC reports have covered
benefits of MDSC technique on biopolymers: reversing and
non reversing signals (C. A. Gracia-Fernandez, Analysis
Thermico Reologia Instruments Co., Madrid, Spain),
biodegradable adhesives (M. J. Escoto, Institute of
Technology, Alicante, Spain), and synthesis, characterization,
and degradation of cyanoacrylate based medical adhesive
specially formulated for strabismus surgery (University of
Alicante, Alicante, Spain).
Poster sessions 1 and 2 have featured most
interesting and important topics.
Poster seesion 1: a comparison of thermal stability,
mechanical properties and structure of nanofibres based
on cellulose and collagen; preparation and characterization
of films of cellulose whiskers crosslinked with a
poly(methyl vinyl ether-co-maleic acid)-poly(ethylene
glycol)matrix; nanocomposite materials containing cellulose
whiskers extracted from palm tree; synthesis by co-grinding
of composites reinforced by cellulose; acylated cellulose
fibres as reinforcing elements in composites with
thermoplastic matrices; bionanocomposites from
polycaprolactone reinforced with cellulose or starch
nanocrystals; fabrication and characterization of
biodegradable plastic based on tapioca starch;
XV
characterization of polypropylene with cassava starch
compounds; renewable materials based on starch, clays
and fine birch pulp fibres; biodegradable composites based
on starch foam and natural fibers; formulation and
characterization of chitosan/whey protein films; new
investigations on the mechanism of thermal polymerization
of vegetable oils and thermomechanical behaviour of
biodegradable plastizicer.
Poster session 2. Physical blends of different
biodegradable aliphatic polyesters to broaden their area of
application; amino acid modified montmorillonite as
reinforcement in polyhydroxybutyrate matrices;
Biodegradable poly(vinyl alcohol)hydrogel membranes
containing nutraceuticals (controlled-release case study);
degradation of polymer and fungal action; modeling
degradation of polymers, biobased composites and
nanocomposites; the research of the biochemical
decomposition of hydrocarbons and polymers using enzymes
to product functional compositions; transport of water as
structurally sensitive process characterizing morphology of
biodegradable polymer system; behaviour of polymer
composites materials under soil microorganisms; synthesis
and properties of biodegradable hybrid polymer based on
peptides and synthetic substances; etc.
The conference has shown that the problems of
biodegradable polymers and sustainable composites are
quite topical and of great importance for pure and applied
chemistry (ResearchàDevelopmentàProduction). The next
(second) conference will be held in 2009 in Italy.
 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 the journal and be written in English. The Journal is
currently accepting articles in such fields as:
· analytical chemistry;
· general and inorganic chemistry;
· organic chemistry;
· physical chemistry;
· chemistry of high molecular compounds;
· materials science and engineering
· chemical kinetics and catalysis;
· technology of inorganic substances;
· technology of organic synthesis products;
· chemical technology of processing of combustible
minerals;
· processes and apparatus of chemical and food
productions;
· biotechnology;
· ecology.
Authors are fully responsible for the content of their
published materials.
Note for Ukrainian authors. Inclusion of an expert
conclusion (the original) and Ukrainian version of manuscript (2
copies) of the article is obligatory.
After the review of the manuscript and acceptance by the
Editor, page proofs are sent to the authors for correction. The
corrected proofs should be returned to the Editorial Board not later
than 5 days upon review receipt. Otherwise the Editorial Board can
decline the article or postpone its publication.
Preparation of the article
Manuscripts have to be submitted in Microsoft Word 97 or
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XVI
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should contain:
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4. Key words should represent content of the whole article and be
characteristic of the terminology used within the particular field
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5. An introduction should be brief and clear and needs to include
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6. All materials and methods by which the results were obtained
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Subheadings may be used.
7. Results should be presented with clarity and precision. The
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Also here subheadings may be used.
8. Conclusions should emphasize the main achievements of this
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Example:
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Nauk Ukrainy, 2007, 66, 198.
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