CC BY
185
УДК 54.05
E. I. Vinhlinskaya, N. R. Prokopchuk, A. L. Shutova, O. V. Stoyanov, O. Yu. Emelina
RESEARCH OF POSSIBLE SYNTHESIS OF ALKYD-STYRENE RESINS
Keywords: alkyd-styrene resins, methods of synthesis, copolymerization, formulations, plant oil, fatty acids of vegetable oils, alkyd resin,
styrene, xylene, initiator, areas of application.
The article covers possible methods of synthesis of alkyd-styrene resins, formulations and areas of application this filmformers in paint production. The article summarizes the main regularities that can help to get in the future alkyd-styrene resins of home production. Possibility ofproduction alkyd-styrene resins at the chemical companies opens wide prospects for creation quick and naturally drying paint materials which will reduce the dependence on imports, provide energy savings and correspondingly increase the competitive ability of products of companies by cheapening of coatings preparation processes.
Ключевые слова: алкидно-стирольные смолы, методы синтеза, сополимеризация, рецептуры, растительного масла, жирные кислоты из растительных масел, алкидные смолы, стирол, ксилол, инициатор, области применения.
В статье охватываются возможные методы синтеза алкидно-стирольных смол, рецептуры и области применения их в качестве пленкообразователей в производстве красок. В статье обобщены основные закономерности, которые могут помочь, чтобы получить в будущем алкидно-стирольные смолы отечественного производства. Возможность производства алкидно-стирольных смол на химических компаниях открывает широкие перспективы для быстрого создания и естественной сушки лакокрасочных материалов, что позволит сократить зависимость от импорта, обеспечит экономию энергии и, соответственно, повышению конкурентоспособности продукции предприятий для удешевление способов получения красок.
Introduction. Currently conventional semi-finished alkyd lacquers dominate in the CIS market among the modified film formers, but in recent years due to the constant rise in energy prices there appeared a demand for paint-and-lacquer materials that reduce energy costs in the preparation of varnish-and-paint coatings.
Energy intensity degradation of coating production can be achieved using natural hardening capable of quick forming of coating (drying time - no more than 30 minutes).
Alkyd-styrene resins are a particular class of film-forming materials which are prepared based on these natural quick drying paints.
Styrenated alkyd resins in comparison with unmodified styrene resins have some advantages: faster drying, increased resistance to water and chemicals, their films are less susceptible to brightness reversion. The disadvantages of such resins include the occurrence of defects during drying and solvent resistance reduction that often result in "blistering" (delamination) during application of a secondary layer. The defect of the upper layers of alkyd-styrene resins is their low endurance, especially to scratching, so they are mainly used in under-coating [1].
This binding group is used in formulas of anticorrosion paints for painting ships, equipment, equalizing compositions and fillings, both one and multi-layer coatings in natural and hot drying [2].
In this regard, there is a constant demand for the film former at the enterprises that they have to meet at the expense of purchase of raw materials in the interna-
tional market. Therefore, the quality and competitiveness of domestic coatings are influenced by such factors as irregular supply, oxidation and loss of raw materials while transporting, as well as the high cost compared with other domestic film formers.
Thus, the creation of alkyd-styrene resins is one of the urgent problems that can both reduce the dependence on import of enterprises and provide energy saving respectively increasing the competitiveness of market at the expense of the cost reduction in coloring process.
Main part. To produce domestic alkyd-styrene resins satisfying the requirements of world standards, we analyzed the scientific literature on the preparation, recipes, as well as the possibilities of application of alkyd-styrene resins in paint-and-varnish production.
Such properties of polystyrene as good coloring maintained unchangable for a long time, the exceptional water resistance, resistance to alkalis and high dielectric properties contributed to intensive search for methods of applying it as a filming. Unfortunately, polystyrene has a number of significant shortcomings along with the good properties.
One of the ways of the removal of shortcomings is to combine its positive properties with substance properties which are film-forming themselves.
Getting styrenated drying oils and alkyd resins created the fourth important group of synthetic products for accelerated drying for decorative and protective coatings in addition to phenolic resins, alkyd resins and nitrocellulose [3].
According to the literature, styrene was polymerized with dehydrated oils in the early 1940s for the first time. The first patent for alkyd resins, modified by styrene was obtained in the UK in 1942 [1].
Styrenated alkyds appeared in commercial quantities in 1948 and occupied a certain place in the fast-drying coatings and hot air drying. Large production capacity of styrene and its relatively low price stimulated its implementation in coating manufacture [4].
The basis of obtaining alkyd-styrene copolymer process is styrene copolymerization reaction with the double bonds of the fatty acid residues of oils [5].
The copolymerization reaction is characteristic for vinyl group. Styrene can be readily copolymerized by any conventional methods: in block or in solution. The process of copolymerization is carried out by heating for 20 hours or more at about 140°C.
Xylene is usually used for copolymerization in the solution. The reaction rate and the amount of the resulting product are changed when xylene is replaced by other solvents. For example, the reaction time increases from 23 to 49 h when xylene is replaced by dipentene. The products obtained from dipentene solution are better aligned but they dry slower. Therefore it is recommended to replace only a part of xylene by dipentene [4].
Limiting styrene content is about 40%. Loading it in large quantities deteriorates compatibility with other film formers as well as it makes worse solubility in solvents; moreover, obtained coatings are brittle. Optimum performance is observed at a ratio of styrene : oil = 40 : 60.
As it is known [6], the molecular weight of the polymer depends on a number of factors - the concentration of monomers, temperature, initiator catalyst content and chain regulators in the reaction mixture, etc. As a means of reducing the concentration of monomer may be its slow introduction (droplet method) into heated to a certain temperature oil, fatty acid oils or alkyd resins. At the same time the decrease in molecular weight will be determined not only by a low concentration of monomer, but also high content of a-methylene groups per injected styrene particle that, in addition, will provide polystyrene chains, significantly enriched with oil component. High concentration of a-methylene groups eliminates the necessity for the introduction of specific growth regulator of circuit. The method of the slow introduction of the monomer allows to obtain homogeneous products with a higher styrene content (up to 70% in the reaction mixture) than conventional mortar method, although a high styrene content (50-70% in the mixture), significantly increases viscosity and reduces elasticity and shock resistance of the films.
A prerequisite to obtain a homogeneous reaction product is the initiator (3-4% by weight of monomer), which contributes not only to accelerate the reaction, but also to decrease molecular weight. As an initiator catalyst of copolymerization process it is better to use alkyl peroxides with relatively high decomposition temperature (tertiary-butyl peroxide). The use of peroxides with low decomposition temperature (lauryl peroxide,
benzoyl peroxide, hydroperoxide of isopropylbenzene) gives a smaller effect [7].
Mixture consisting of styrene and a-methyl styrene enables to obtain homogeneous light products with a large number of oil. The ratio between a-methylstyrene and styrene is usually 3 : 7. a-Methylstyrene is very helpful to get compatible products, moderating reaction and slowing entry of styrene into copolymer.
Thus, one must regulate the quantitative ratios of the reactants in the copolymerization reaction, considering type and amount of initiator catalyst, temperature and solvent, if copolymerization is carried out in solution. Technically homogeneous products can be obtained when applied the same process conditions.
As the literary analysis showed, fundamentally different methods for alkyd-styrene copolymers are possible:
1) copolymerization of fatty acids of vegetable oils with styrene and further reacting of the obtained copol-ymer with other components of alkyd oligomers (phthalic anhydride, glycerol) by fatty acid method (method 1);
2) copolymerization of the styrene oil and the subsequent synthesis of the alkyd by the method of using the glyceride with oil copolymer (method 2);
3) copolymerization of monoglycerides with styrene and their further esterification (method 3);
4) copolymerization of preformed alkyd with styrene (method 4).
According to method 1 preparation of an alkyd-styrene resin can be represented as the simplified scheme shown in Fig. 1.
vacuum distillation
Fig. 1 - The scheme for producing alkyd-styrene resin according to method 1
A number of papers concern studying the process of copolymerization of styrene with fatty acids of vegetable oils. In particular, the copolymerization of styrene with a-eleostearic acid which has three conjugated bonds is under consideration. Tung oil is unique in content of eleostearic acid (80%). This research has made it possible to explain the mechanism of formation of styrene copolymers with fatty acids containing conjugated double bonds.
In this case, this reaction proceeds as in the copoly-merization of styrene-butadiene: styrene-butadiene attachment occurs primarily in the 1,4-position, and chain growth of styrene via dienes [8].
Thus, the fatty acids with conjugated double bonds in the molecule (eleostearic, 9,11-linoleic) form two types of products with styrene - the true copolymers of high molecular weight (Fig. 2), and adducts of the
Diels-Alder (diene synthesis) formed in the addition of styrene to fatty acid in a molar ratio of 1 : 1 (Fig. 3) [7].
—CH2—CH=CH—CH=CH— + 2n C6H5CH =CH3—-
-- —СН,—CH-CH=CH-CH—
J
Ген,—CH
Fig. 2 - The scheme for producing alkyd-styrene copolymers
^ch2—ch yh-ch^ nch2-ch'
6
Fig. 3 - The adduct of the Diels-Alder
This paper of Shneyderova V. V. deals with copoly-merization of styrene with linoleic acid containing two isolated double bonds (9,12-linoleic acid), which is one of the main components of most drying and semidrying oils. Polymerization was accomplished in sealed nitrogen-filled glass ampoules at 150°C with benzoyl peroxide (1% of styrene content) and the molar ratios in the mixture of styrene and linoleic acid 94 : 6, 90 : 10, 86 : 14 and 80 : 20. This paper shows that increasing the molar proportion of fatty acid in the initial reaction mixture dramatically increases the percentage of low molecular weight copolymers of styrene with linoleic acid [9].
It is known [4] that the tung oil acids react with styrene slower than acid of oiticica oil. Dehydrated castor oil acids react with styrene with the greatest reaction rate. It is hard to explain, because tung oil has the greatest number and the greatest degree of conjugacy of double bonds. Perhaps the reason for this phenomenon is almost complete copolymerization of styrene with tung oil acids. Because of this, the polymerization of the styrene with the greatest reaction rate occurs to a lesser extent with formation of a certain amount of polystyrene. Since the reaction rate of polymerization styrene is higher than the reaction of copolymerization the styrene flow rate at a particular time must be greater using dehydrated castor oil acids.
The formulation and technique [4] of obtaining styrene acids of dehydrated castor oil are known (Table 1).
Table 1 - Formulation of styrene acids of dehydrated castor oil
According to this recipe, dehydrated castor oil acids are heated in a flask with stirrer and cooler to 115°C; then when stirred, a mixture of styrene with a catalyst is added for an hour and the temperature raises during this time to about 145°C. This temperature is maintained for 30 minutes, after that the unreacted styrene is subjected to vacuum distillation.
When acids of dehydrated castor oil were styrenated it was established that if all components are all heated, rapid exothermal reaction occurs at 120°C. The product obtained is thus turbid and inhomogeneous representing an incompatible mixture of unreacted fatty acids, a quantity of styrenated acids and a considerable amount of polystyrene. The product formed by slow addition of a mixture of styrene with the catalyst to fatty acids becomes transparent and homogeneous. The presence of free polystyrene is not determined, but it was established that with increasing amounts of loaded styrene the amount of styrene reacting with fatty acids increases. At the same time the molar ratio of styrene to fatty acid is 4 : 1, taken in formulation (see Table 1), is considered to be optimal.
The formulation of obtaining of alkyd resins, modified by styrene for synthesis according to method 1 is also known (Table 2) [10].
Table 2 -- Formulation of alkyd-styrene resin for synthesis according to method 1
Components Component content, wt %
acids of dehydrated castor oil 34.S
Styrene 24.4
a-Methylstyrene 10.4
Glycerine 13.1
Phthalic Anhydride 17.3
Total 100.0
Note. Initiator - 2% benzoyl peroxide (from styrene content).
Deriving alkyd styrene resin according to method 2 (Fig. 4) is under consideration.
vacuum distillation
Components Component content, wt %
Acids of dehydrated castor oil 40.9
Styrene 59.1
Total 100.0
alkyd-styrene resin
pi 111 ItlllL
anhydride
Fig. 4 - The scheme for producing alkyd-styrene resin according to method 2
It is known [8] that in 1946 a mechanism of co-polymerization of oils with styrene was proposed which is different for oils with isolated and conjugated double bonds. In the first case, the oil serves as a chain transfer agent, playing the same role as the solvent. In the presence of oils with isolated double bonds chain stopping can occur due to unstable hydrogen of the methylene group located in the aposition to the double bond.
Drinberg A. Ya., Fundyler B. M. and Lifits L. A. have also investigated the copolymerization of sty-
Note. Initiator - 3% benzoyl peroxide (from styrene content).
rene with vegetable oils. They found that the copol-ymerisation reaction runs only with tung oil containing a conjugated bond system. Linseed oil is possible to introduce into the copolymerization reaction, being preoxidized by atmospheric oxygen. Crude sunflower oil as well as oxidized do not enter in the copolymer-ization reaction with styrene. Copolymerization reaction takes place only when oxidized mixtures of sunflower and tung oils are used together and it is sufficient to introduce 5% of tung oil. It is also established that the rate of conversion into a three-dimensional polymer increases with increasing styrene content in the copolymer [11].
Polystyrenes have relatively low melting, but at normal temperature they are incompatible with the oil. Homogeneous product is formed when oil styrene monomer is heated with reflux condenser and peroxidate catalyst as a result of copolymerization, which proceeds readily with oils having conjugated bonds, and only to a small extent with oils having nonconjugated bonds [4].
A high content of conjugated double bonds in oils, during their copolymerization with styrene can easily cause gelation as a result of the formation of spatial polymers due to crosslinking radicals of fatty acids [8].
Styrene and oil can be copolymerized either in solution or in block. Copolymerization in solution makes it possible to control the process well, but it is slow and, of course, if you need a product without solvent, it must then be removed. Usual formulation comprises 25 parts of oil, 25 parts of styrene and 50 parts of solvent. The mixture is heated until the
desired degree of conversion. The residual monomer styrene can be distilled to remove, and it is accompanied by removal of most solvent, which requires subsequent addition of fresh solvent.
Block copolymerization proceeds much faster than in solution, but in this case styrene polymerizes itself readily as well as it copolymerizes. When co-polymerized by this method, the products are incompatible and turbid due to the incompatibility of polystyrene with oil. Therefore, to obtain bright and homogeneous products it is recommended to use a mixture of styrene and a-methylstyrene [3].
Table 3 shows the possible formulations of styrenated oils and describes the technological copolymerization process in the block.
The table shows that almost all the copolymeri-zation products dry quickly, except made by a mixture of soybean and tung oils. The films produced from a mixture of 50% linseed and 50% dehydrated castor possess the best drying ability. However, the least time-consuming process is the copolymeriza-tion of dehydrated castor oil with a mixture of styrene and a-methylstyrene.
The formulation [5] of obtaining alkyd-styrene resins with oxidized soybean oil according to method 2 is known (Table 4).
Alkyd-styrene resins obtained by this formulation have an acid number of not more than 16 mg KOH/g. The films of these alkyds dry at (20 ± 2)°C to degree 1 for 22 minutes, and up to degree 3 for not more than 8 hours. They have good elasticity, and resistance to water, alkalis, and solvents.
Table 3 - Features of copolymerization process in the block according to method 2
Composition of the mixture of oils, wt %
Components 100% dehydrated castor 90% linseed 10% tung 80% soybean 20% tung 50% linseed and 50% dehydrated castor
Formulations of styrenated oils
Oil 45 45 45 50
Mixture of styrene and a-methylstyrene 55 55 55 50
Reaction time, h
Addition of styrene 6 6 6 6
Temperature rise to 250°C 5 6 4 5
Exposure at 250°C 6 6 6 7
Heating 250-285°C 0.5 - - -
Heating 250-300°C - 0.5 0.5 1
Exposure at 285°C 1.5 - - -
Exposure at 300°C - 2.5 3.5 3
Overall process 19 21 20 22
Rates of obtained styrenated oils
Amount of unreacted styrene, % 1.2 1.5 2.0 1.2
Drying time at temperature (20 ± 2)°C, h, not more: a) to degree 1 0.75 1 2.5 0.5
b) to degree 3 6.0 7.0 24 5
Notes. In all cases before styrene adding oil was heated to 160°C. Initiator - 3% benzoyl peroxide (from styrene content). Solidification was carried out with a mixture of desiccants: 0.5% Pb and 0.02% Co based on the weight of metal to oil. The dilutant was a mixture of 70% mineral spirits and 30% solvent resulted in obtaining of 60% solution.
Table 4 - Formulation of alkyd-styrene resin for the synthesis according to method 2
Components Component content, wt %
Oxidized soya bean oil 37.7
Styrene 19.1
a-Methylstyrene 8.2
Glycerine 10.9
Phthalic anhydride 24.1
Total 100.0
Notes. Initiator - 3% benzoyl peroxide (from styrene content). The reaction of transesterification was carried out with 0.01% (based on the oil content) of calcium oxide.
Another known method of obtaining styrenated al-kyds (method 3) consists in styrenating of monoglycerides and their subsequent esterification (Fig. 5).
plant oil glycerine
vacuum distillation ,
styrene excess monoglycerides styrene
water styrene monoglycerides *- phthalic anhydrate
alkyd-styrene resin
Fig. 5 - The scheme for obtaining of alkyd-styrene resins according to method 3
Table 5 shows the formulation of alkyd-styrene resins with a mixture of linseed and dehydrated castor oils to obtain alkyd-styrene resin [5].
Table 5 - Formulation of alkyd-styrene resin for the synthesis according to method 3
Components Component content, wt %
Linseed oil 19,0
Dehydrated castor oil 19.0
Glycerine 8.7
Styrene 35.0
Phthalic anhydride 18.3
Total 100.0
Notes. The reaction of transesterification was carried out with 0.06% (based on the oil content) of calcium oxide. 4.62% (by weight basis) of xylene was added for azeotropic distillation of water of reaction. Copolymerization reaction initiator - 0.85% (the content of the styrene) of cumene hydroperoxide (73% solution in xylene).
According to the formulation given in Table 6, the process of preparation of styrenated alkyd consists of several stages:
1) alcoholysis of oils: linseed and dehydrated castor oil, glycerol and calcium oxide is heated to 230°C and kept at that temperature for about 1 hour to obtain a product which is soluble in methanol, 1 : 3;
2) styrenazing of monoglycerides: the half part of the styrene and the initiator solution are added to monoglycerides and the mixture is heated to 160°C, then a reflux condenser on and the residue of styrene is added for 3 hours. Then in the next 4-5 hours the temperature is raised to 210°C;
3) esterification for obtaining of the styrenated al-kyd: phthalic anhydride is added to styrenated monoglycerides and xylene is added for azeotropic solution. The mixture of these substances is heated at 215-230°C for about 3 hours to achieve the required viscosity and acid number, after which the resin is dissolved and filtered.
Such a styrene-alkyd resin has an acid number of not more than 7 mg KOH/g. Films of alkyds dry at (20 ± 2)°C to 1 degree for 10 minutes.
The most common method of obtaining industrial alkyd-styrene resins is method 4 (Fig. 6).
Low-viscosity alkyd is used for copolymerization with styrene. Homogeneous resins with good properties are obtained when applying medium fatty alkyd resins. Fatty acids with conjugated double bonds, are used, un-saturated dibasic acids or a mixture of saturated dibasic acids with a small amount of maleic anhydride are used in the synthesis of alkyd.
vacuum
distillation *-
styrene excess
alkyd resin
styrene
alkyd-styrene resin
Fig. 6 - The scheme for obtaining alkyd-styrene resin according to method 4
Maleic anhydride is involved in the reaction of a polyesterification and serves the source of both double bonds necessary for copolymerization with styrene. The maleic anhydride content in alkyd should be precisely calculated. Optimal conditions for the copolymerization are provided for the introduction of maleic anhydride in the amount that one double bond of maleic anhydride is on 3 molecules of phthalic anhydride. In this case the final product is transparent and has a relatively stable viscosity [12].
Further copolymerization process is carried out at the temperature from 140 to 170°C in xylene with initiator. The main initiator is di-tret-butyl peroxide, the amount of which depends on the temperature and varies from 1 to 4% from weight of monomer. Pre-oxidation and polymerization of oils (linseed, sunflower) increases the yield of the copolymer. The copolymerization involves the method, in which styrene is gradually introduced into the mixture for several hours together with an initiator. After addition of monomers and initiators the reaction temperature is maintained; the degree of conversion is determined by measuring the mass of the non-volatile part. If necessary, for the completeness of the reaction a small amount of initiator is additionally injected. The quantitative ratio of the alkyd resin and the copolymer is generally from 60 : 40 to 85 : 15. The re-
action is usually carried out until it terminates at 9597%. The residue of unreacted styrene is removed under suction at the end of the process.
To improve the odor and light-fastness it is desirable to remove small amounts of residual monomer styrene. For this, C02 is blown through the reaction product before it is left to cool. The content of volatile substances in the drying oils is negligible, and thus, the degree of conversion can be estimated by collecting matter removed by blowing [3].
The formulation of a styrene-alkyd resin for synthesis based on glyptal resin is known by method 4 (Table 6) [13]. Xylene solution of glyptal resin (50%), styrene and xylene are placed into flask. The resulting mixture is stirred for 30 min and is heated. When temperature runs up to temperature 140°C, 50% solution of t-butyl peroxide or other peroxide in xylene is given into the reaction mixture in four equal portions at intervals of 1.5 h. Aggregate exposure is carried out at 140°C for 20-25 h to obtain a dry residue 49.5-50.0%. The viscosity of the reaction solution should be 45-50 seconds. Then the solution is cooled to room temperature and filtered. Alkyd-styrene resin obtained by this formulation has an acid value of not more than 7 mg KOH/g, the drying time up to 3 degrees at (20 ± 2)°C - less than 8 hours.
Table 6 - Formulation of alkyd-styrene resin for the synthesis according to method 3
Depending on the styrene content styrene-alkyd resins can be divided into 3 groups [7]:
1) resins containing 30% of styrene and more; they dry faster, diluted with white spirit and are suitable after dilution for brushing. On the basis of these resins solid, water-resistant, fast drying coating are obtained (drying from dust for 20 minutes, the real drying 1.5 h). Lacquers and enamels, based on these resins have a high concentration of film-forming substance and they may be applied for painting the chassis of motor vehicles, heavy machinery and equipment, cables, decks, etc.;
2) resins containing 15-25% of styrene are used in the primers and in baking enamels. Particularly their use is appropriate with melamine-formaldehyde resins with which they conjunct well. The obtained coatings of drying possess high hardness, luster, resistance to water, alkalis and detergents, as well as weather resistance. They can be used for dyeing of washing machines, etc.;
3) resins containing 10% of styrene are well diluted with white spirit, and can be brushed. These resins can be used for colouring of the inside of a building.
Alkyd-styrene resins are available as solutions in white spirits or xylene. For quick hardening films of air drying xylene solution is more profitable, but for grinding pigments and improving coatings with high gloss the solution in slowly evaporating white spirit should be applied [4].
Film formation occurs primarily through physical drying (evaporation of solvent), as well as oxidative polymerization due to the remaining double bonds of the fatty acid residues of oils. Air curing is carried out with siccatives [14].
It is known [4] that usual combination of lead and cobalt driers are added to the coatings of air-drying based on styrenated alkyds. The amount of the metal input depends on the type of pigment, as well as in conventional oil and alkyd lacquers. In styrenated alkyds, drying at 120°C or below a small amount of cobalt is put, and in styrenated alkyds drying at a temperature above 120°C driers are not usually put.
Conclusion. This paper deals with possible methods of obtaining, formulations, as well as the possibility of applying alkyd-styrene resins in paint and varnish production.
On the basis of this work one can distinguish 4 main methods of the synthesis of alkyd-styrene resins which have their own characteristics, advantages and disadvantages. But the most common method is copol-ymerization of alkyd with styrene.
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Components Component content, wt %
Glyptal resin (50%-concentration) 50.0
Styrene 25.0
Xylene 25.0
Total 100.0
Note. Initiator - 2% tertiary butyl peroxide (from styrene content).
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© E. 1 Vinhlinskaya - Ph. D student, junior scientific researcher, Belarusian State Technological University, Minsk, Belarus, [email protected]; N. R. Prokopchuk - Corresponding Member of Belarusian National Academy of Sciences, Doctor of Chemical Sciences, Professor, Head of Department, Belarusian State Technological University, Minsk, Belarus, [email protected]; A. L. Shutova - Candidate of Technical Sciences, Assistant professor, Belarusian State Technological University, Minsk, Belarus, [email protected]; O. V. Stoyanov - Doctor of Technical Sciences, professor, Department of technology of plastic materials, Kazan National Research Technological University, Kazan, [email protected]; O. Yu. Emelina - Candidate of Chemical Sciences, assistant, Department of technology of plastic materials, Kazan National Research Technological University, Kazan, Russian Federation, e-mail: [email protected].
© E. И. Винглинская - аспирант, младший научный сотрудник, Белорусский государственный технологический университет, Минск, Белоруссия, [email protected]; Н. Р. Прокопчук - Член-корреспондент белорусской Национальной академии наук, доктор химических наук, профессор, заведующий кафедрой, Белорусский государственный технологический университет, Минск, Белоруссия, [email protected]; А. Л. Шутова - кандидат химических наук, доцент, Белорусский государственный технологический университет, Минск, Беларусь, [email protected]; О. В. Стоянов - доктор технических наук, профессор, заведующий кафедрой Технологии пластических масс, Казанский национальный исследовательский технологический университет, Казань, Российская Федерация, [email protected]; О. Ю. Емелина - кандидат химических наук, ассистент кафедры Технологии пластических масс, Казанский национальный исследовательский технологический университет, Казань, Российская Федерация, [email protected].
