UA80727C2 - Process for preparation of chemically modified molybdenum trisulfide nanoparticles and derivatives thereof (variants) - Google Patents

Abstract

A process for preparation of molybdenum trisulfde nanoparticles and derivatives thereof from salts of thiomolybdenum acid of the general formula of M2MoS4-xOx, where M - NH4, Na, x = 0-3, or from salts of molybdenum acid of the formula of M2MoO4, where M - NH4, Na, and sulphur donor in the presence of two modifiers, from which there are used as the first tetralkylammonium salts or mixtures of salts of the general formula of R1R2R3R4NX, where R1, R2, R3 and R4 - same or different, are chosen of C1-C16 alkyls, X - Cl, Br, and as the second there are used derivatives of succinimide of the general formula 1, where R5 is normal or branched alkyl or oligoalkylene with molecular weight between 140 and approximately 1000, R6 are selected from the group: H, -C(=O)NH2, -(CH2CH2NH)nCH3, n = 1-4, at that the process is carried out by thermal treatment of homogenized in the polar solvent of the salt of thiomolybdenum acid of second modifier, cooling the obtained mixture and subsequent addition of second or first modifier, respectively. Such sulphur-containing molybdenum compounds are used as additives to lubricant materials reducing friction coefficient. 1

Description

Description of the invention

The invention relates to the field of petrochemicals, more specifically, to sulfur-containing compounds of molybdenum and their use as additives to lubricants that reduce the coefficient of friction.

It is well known that antifriction additives (friction modifiers) are introduced into lubricants to save fuel consumption and to reduce the wear of machine parts during friction. It is also known that lubricant-soluble complex compounds of molybdenum, which include sulfur, nitrogen or phosphorus atoms as ligands, are used as friction modifiers.

So, for example, the US patent (1) describes a method of obtaining a lubricant additive based on tetraalkyl(alkenyl)ammonium thiomolybdate 70, which improves the antifriction properties of the lubricant. Disadvantages of the proposed method include the use in the composition of one of the starting components, namely tetraalkylammonium halides, as hydrocarbon radicals of rather difficult and expensive alkyl and alkenyl groups of vegetable oils and fats, for example, cocoa butter or soybean oil.

Method |2) is known, in which lubricant additives are obtained by the reaction of a sulfur-containing organic compound having 12 mobile hydrogen atoms with molybdenum pentachloride. The product isolated as a result of the reaction contained 390 molybdenum and about 195 chlorine, which is undesirable for environmental reasons and because of the possible corrosive activity of the product.

A molybdenum-containing additive to lubricants that exhibits antifriction and antioxidant properties is obtained, as described in the US patent |Z, in three stages, where in the first stage the reaction of triglyceride is carried out in a plant-based way: oil with a nitrogen-containing compound, in the second - the interaction of the product with a molybdenum compound and on the third - the reaction of the obtained product with sulfur or with a sulfur-containing compound. Disadvantages of the method include a rather complicated synthesis path (multistage, presence of an inert atmosphere, strictly limited temperature intervals).

Known methods (4, 5) where lubricant additives are obtained on the basis of molybdenum dithiocarbamine complexes.

These additives have multifunctional (including antifriction) properties, but their synthesis is quite complex and involves the use of toxic reagents, for example, carbon disulfide. c 29 A known method according to which an additive to lubricants is obtained on the basis of a mixture of the friction modifier Ge) (a nitrogen- or oxygen-containing organic compound) with a trinuclear sulfur-containing complex of molybdenum, which includes dithiocarbamine groups as ligands (6). The disadvantages of the method include the complex composition of the additive and the multi-stage synthesis of the molybdenum organocompound.

The closest analogue of the claimed invention is the method (7), in which the antifriction additive is obtained in the form of chemically modified nanoparticles of molybdenum trisulfide. In this method, nanoparticles of molybdenum trisulfide are obtained by forming inverted "water-in-oil" tin microemulsions stabilized by surface-active substances and containing water-soluble salts of molybdenum acid in the aqueous phase, in their conversion into salts of thiomolybdenum acid by reaction with hydrogen sulfide and subsequent release of Ha nanoparticles »)

Mo5z, pre-treated with modifying compounds. As a result, stable hydrocarbons are obtained

From media, including lubricants, nanoparticles of molybdenum trisulfide, which show high efficiency as antifriction additives. The disadvantages of this method include the low manufacturability of the synthesis of the additive, which is associated with carrying out the process in highly diluted organic solutions and using hydrogen sulfide as a reagent. "

The task of the intended invention is to develop a convenient and technological method of obtaining an additive to C lubricants based on chemically modified nanoparticles of molybdenum trisulfide and its derivatives. c To solve the problem, this method of obtaining an additive to lubricants is proposed, which provides two variants of its implementation.

According to the first option, in the method of obtaining an additive to lubricants based on chemically modified nanoparticles of molybdenum trisulfide and/or its derivatives, nanoparticles of molybdenum trisulfide and/or its derivatives are obtained from thiomolybdic acid salts of the general formula МоМо5, ХО,, where М-МН, . , -1 which includes C.4-C.v alkyl, X - CI, Bg, and as the second - succinimide derivatives of the general formula mo o ! "M k-Y m-y o 7 de B? - normal or branched alkyl or oligoalkylene with a molecular weight from 140 to approximately

ГФ) 1000, E9 is selected from the group that includes Н, -С(-О)МН», -"СНоСНоМН) СНа, p-1-4, and the process is carried out by heat treatment of a mixture of thiomolybdic acid salt homogenized in a polar solvent and of the first or second modifier, cooling the resulting mixture and subsequent addition of the second or first modifier, respectively. 60 The second embodiment of the method according to the invention consists in the fact that nanoparticles of molybdenum trisulfide or its derivatives are obtained from molybdic acid salts of the formula MoMoO,), where МАМН,, Ma and the sulfur donor, as such, use an inorganic sulfide or polysulfide of the general formula M'oZ, where М'ЕМН,, Ma, n-1-4, or thiourea, in the presence of two modifiers, of which tetraalkylammonium salts or mixtures of salts of the general formula К'В2ВЗВ"МХ, where В", 2, ВЗ and 7, are used as the first, are the same or different, choose from the groups that include C.4-C.b alkyl, X - CI, Bg, and as the second - succinimide derivatives of the general formula o , vrnia o where B? - normal or branched alkyl or oligoalkylene with a molecular weight from 140 to about 1000, 9 is selected from the group that includes Н, -С(-О)МН»о, "СНоСНоМН) СН, н-1-4, and the process is carried out by heat treatment of a mixture of molybdic acid salt homogenized in a polar solvent, a sulfur donor, such as inorganic sulfide, polysulfide or thiourea, and the first or second modifier, cooling the resulting mixture and subsequent addition of the second or first modifier, respectively.

In the proposed method, according to any version of implementation, heat treatment is carried out at a temperature of 150-2202C for 1-2 hours, and methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, acetone or benzene.

The tetraalkylammonium salt is selected from the group that includes tricaprylmethylammonium chloride (Aliquat 336), metaltrialkyl(Cn-Si)ammonium chloride (Adogene 464), cetyltrimethylammonium bromide (CTAB).

The derivative of succinimide, which is used as a second modifier, is mainly a product of alkylation of succinimide with a mixture of oligomers of olefins, which is produced industrially. Such a mixture consists of a wide range of compounds, including derivatives with various hydrocarbon radicals of different lengths and structures (normal or branched). In particular, this product can be, for example, dispersible additive S-BA, TU 38.101146-77, M content 1.795, viscosity at 1002C no more than 420mm2/s.

The product obtained according to any variant of the method is filtered to separate solid impurities and the remains of volatile organic solvents are removed in a vacuum. The entire production process can be carried out in one vessel without intermediate stages of separation and/or purification, without the involvement of large quantities of organic solvents. Go)

The obtained product is a viscous liquid of dark brown color, which is easily mixed with hydrocarbons and petroleum lubricants to form transparent solutions or compositions having a color from red-brown to brown. The content of molybdenum in the product usually ranges from 0.5 to 2.095 wt.

The solutions of the obtained product are stable dispersions of surface-modified nanoparticles - molybdenum trisulfide, which is confirmed by the data of electronic spectroscopy in the UV and visible region (Fig. 1) and Ga small-angle scattering of X-rays (ХАХ5) (Fig. 2). The 5BAH5 method allows you to determine the size of the inorganic core of nanoparticles, which are in the range from 1 to bnm and, unlike the surface-modified nanoparticles described in |7|І, are characterized by a monodisperse size distribution. The last circumstance makes it possible to induce a higher degree of reproducibility of the synthesis. 3o The following examples illustrate the present invention, but in no way limit its scope. co

Example 1

The homogeneous mixture obtained by stirring at 60 9 0.12 g of ammonium tetrathiomolybdate, 3.0 g of methyltrialkyl(Cn-SiO)ammonium chloride (Adogen? 464) and 5 ml of methanol is subjected to heat treatment at 20022 °C for 2 hours, the remaining product is 3095 total initial mass of components. The product is cooled to a temperature below 502C. 4.2 g of the succinimide derivative - a dispersing additive with C-5BA, and 5 ml of chloroform are added to the remaining product, mixed with a magnetic stirrer, filtered through a "blue tape" filter, and the solvent :c" is removed under vacuum. The content of molybdenum in the product is 1.2295. In the UV spectrum of the obtained product, there are no absorption bands corresponding to ammonium tetrathiomolybdate.

Example 2 y y y y y co The homogeneous mixture obtained by stirring at 60 9 0.12 g of ammonium tetrathiomolybdate, 3.0 g of tricaprylmethylammonium chloride (Aliquot 336) and 5 ml of methanol is subjected to heat treatment at 2002С for 2 hours, the remaining product is 2995 total initial mass of components. The product is cooled to -I temperature below 5020. 4.2 g of succinimide derivative - dispersing additive С-5А 5р is added to the product residue | ml of chloroform, stir with a magnetic stirrer, filter as in item 1, remove the solvent under vacuum. The content of molybdenum in the product is 1.2595. "And Example Z

The homogeneous mixture obtained by mixing at 60 9 0.12 g of ammonium tetrathiomolybdate, 3.0 g of cetyltrimethylammonium bromide (CTAB) and 1 Oml of a mixture of methanol-chloroform 1:1 is subjected to heat treatment at 2009 for 2 hours, the product residue is 5590 of the total initial weight of the components. The product is cooled to a temperature below 5023. 4.2 g of succinimide derivative - a dispersing additive about C-5BA, and 5 ml of chloroform are added to the product residue, mixed with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.365.

Example 4 60 Homogeneous mixture obtained by stirring at 602 0.12 g of ammonium tetrathiomolybdate, 1.5 g of TsAB and 1.5 g

Adogenf and 10 ml of a mixture of methanol-chloroform 1:1, subjected to heat treatment at 2002C for 2 hours, the remaining product is 42905 of the total initial weight of the components. The product is cooled to a temperature below 5096.

4.2 g of succinimide derivative - dispersing additive C-5A, and ml of chloroform are added to the product residue, mixed with a magnetic stirrer, filtered, and the solvent is removed under vacuum. The content of molybdenum in the product is 1.3895.

Example 5

The homogeneous mixture, obtained by stirring at 602 0.12 g of ammonium tetrathiomolybdate, 3.0 g of Adogene and 5 ml of methanol, is subjected to heat treatment at 1802 for 2 hours, the remaining product is 2995 of the initial weight of the components. The product is cooled to a temperature below 502. 4.2 g of succinimide derivative - dispersing additive C-5A and 1 ml of chloroform are added to the product residue, mixed with a magnetic stirrer, filtered, and the solvent is removed under vacuum. The content of molybdenum in the product is 1.19905.

Example 6

The homogeneous mixture obtained by mixing at 602 0.12 g of ammonium tetrathiomolybdate, 3.0 g of Adogene and 5 ml of methanol is subjected to heat treatment at 2102 C for 2 hours, the remaining product is 27.595 of the original mass of 70 components. The product is cooled to a temperature below 5020. 4.2 g of succinimide derivative - dispersing additive C-5A and 5 ml of chloroform are added to the remaining product, mixed with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.2596.

Example 7

The homogeneous mixture obtained by mixing at 602 0.24 g of ammonium tetrathiomolybdate, Z.Og Adogene and 5 ml of 75 acetone is subjected to heat treatment at 2002С for 2 hours, the remaining product is 26.296 of the initial weight of the components. The product is cooled to a temperature below 502. 4.2 g of succinimide derivative - dispersing additive C-5A and bBml of chloroform are added to the product residue, mixed with a magnetic stirrer, filtered, and the solvent is removed under vacuum. The content of molybdenum in the product is 2.9296.

Example 8

The homogeneous mixture obtained by stirring at 602 0.12 g of ammonium tetrathiomolybdate, 3.0 g of Adogene and 5 ml of methanol is subjected to heat treatment at 2002 for 2 hours, the remainder of the product is 28.295 of the initial weight of the components. The product is cooled to a temperature below 509С. 4.2 g of succinimide derivative urea and ml of chloroform are added to the remaining product, mixed with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.22965.

Example 9 Fr

The homogeneous mixture obtained by stirring at 602 0.24 g of ammonium tetrathiomolybdate, 3.0 g of Adogene and 5 ml of methanol is subjected to heat treatment at 2002 for 2 hours, the remaining product is 30.195 of the original total weight of the components. The product is cooled to a temperature below 5022. 42 g of r. is added to the residue

M-alkylenamine derivative of succinimide and 5 ml of chloroform, mix with a magnetic stirrer, filter, remove the solvent under vacuum. The content of molybdenum in the product is 1.19905. with

Example 10 rch-

The method of preparation according to example 1, which differs in that ethanol is used instead of methanol.

Example 11 -

The method of preparation according to example 1, which differs in that propanol is used instead of methanol. with

Example 12

The method of preparation according to example 1, which differs in that instead of methanol, isopropanol is used.

Example 13 "

The method of preparation according to example 1, which differs in that n-butanol is used instead of methanol.

Example 14 - c The method of preparation according to example 1, which differs in that isobutanol is used instead of methanol. ц Example 15. "» The method of preparation according to example 1, which differs in that instead of methanol, sec-butanol is used.

Example 16. (ee) The method of preparation according to example 9, which differs in that instead of ammonium tetrathiomolybdate, ammonium trithiomolybdate is used. o Example 17. -I Method of preparation according to example 9, which differs in that instead of ammonium tetrathiomolybdate, ammonium dithiomolybdate is used. where Example 18. "I Method of preparation according to example 9, which differs in that instead of ammonium tetrathiomolybdate, ammonium monothiomolybdate is used.

Example 19

The homogeneous mixture obtained by mixing at 602 0.0095g of ammonium molybdate and 0.0113g of Ma»5.9NoO and 0.0360Og of AdogenfF in 1 ml of benzene is subjected to heat treatment at 2002 for ZOkhv. The remainder of the product after o heat treatment is 4895 of the total mass of the original components. The product is cooled to a temperature below (name) 5020. 4.2 g of succinimide derivative - dispersing additive C-5A, one ml of chloroform are added to the product residue, mixed with a magnetic stirrer, filtered through a "blue tape" filter, then the solvent is removed under vacuum. 60 The content of molybdenum in the product is 1.3595.

Example 20

The method of preparation according to example 1, which differs in that, first, 0.12 g of ammonium tetrathiomolybdate and 4.2 g of succinimide derivative - dispersing additive C-5A are homogenized, the mixture is subjected to heat treatment at 180-2002 C for 1 hour, then 3.0 g is added to the residue AdogenuF, homogenize and subject to heat treatment at 180-2002C for 1 hour. The product is cooled to a temperature below 502C. The residue is dissolved in chloroform, filtered, and the solvent is removed under vacuum. As a result, a product with a molybdenum content of 0.6695 is obtained.

Example 21

The homogeneous mixture obtained by mixing at 602 0.0102 g of ammonium molybdate, 0.0320 g of AdogenudF and 0.0101 g of thiourea and 5 ml of benzene is subjected to heat treatment at 2002 for 2 hours. The remainder of the product after heat treatment is 43.09% of the total mass of the initial components. The product is cooled to a temperature below 502C. Add 1 ml of chloroform, 0.042 g of succinimide derivative - a dispersing additive to the residue and mix with a magnetic stirrer, filter and then evaporate the solvent in a vacuum. The content of molybdenum in product 70 is 2.35905.

Example 22

A homogeneous mixture obtained by stirring at 602 0.0101g of ammonium molybdate, 0.0315g Adogenf, 0.0145g

Ma»52Oz5.5H2O and Bml of benzene, subjected to heat treatment at 2002 for 2 hours. The product residue after heat treatment is 39.0956 of the total mass of the original components. The product is cooled to a temperature below 5020. The product is cooled to a temperature below 5020. 5 ml of chloroform, 0.042 g of succinimide derivative - a dispersing additive are added to the residue and mixed with a magnetic stirrer, filtered and then the solvent is evaporated in a vacuum. The content of molybdenum in the product is 1.31965.

Example 23

The homogeneous mixture obtained by mixing at 602 0.24 g of ammonium tetramolybdate, 3.0 g of Adogene and 5 ml of a mixture of methanol:benzene, 1:11, is subjected to heat treatment at 2009С for 2 hours, the remainder of the product is 30.096 of the initial total weight of the components. The product is cooled to a temperature below 5092C. 4.2 g of succinimide derivative - dispersing additive C-5A and ml of chloroform are added to the residue, mixed with a magnetic stirrer, filtered, and the solvent is removed under vacuum. The content of molybdenum in the product is 1.29965.

All results are collected in a table. with o

Example | Thiomolybdic acid salt Quaternary ammonium salt | Inorganic sulfide | Derivative

Mo (amount, g) base solvent (amount, g) (amount, g) succinimide | synthesis

MO оон and и сх ША 1.96 с схло хндоМмова олоунемае don яви) 0000 Чем 000000 p) 600200 2 (хндmovilametnoi Alquat ze ope 2yu in z (multiple SHABO 00000000 50020 о z (Mndmovy tet TSABAvyaenI 50 ee 120020 » Avenue Avenue CO 5 (Avenue Avenue Gnovement 7 Hnova Avenue Avenue 8 (Avenue Avenue 00000000 20250020, 9 (HNDMOVILIMETNOY ABOUT 000000000000 (хноомова Олоустотнол Авоен 00000000 ною 5 хномова оовунеитноя Авеню не ля (омова олзувюбутют (Адожн 00000000 120 2ю 5 (хнаомова Олоувюрвуто Аяяеня 00000000 ною о тв (хндрмоову Олгуметно (Авочніїо 00000000 50020 - з іхнамоорво олвуметеной Адочнії 0000пеже 00000022 5002ю че ВЕСНИ ет НИ З ЛИН with NN NOT PSY VEN 5 (khnayumotom Oobyusuvenyu Adoen 005 000 av oope 00011009 o02yu y. 25 (khnaomova oobunetya Avenue 2 chnayumotom Oobyumotom Oobyusuvenyu Adoen00U 00Tooeyuene 000 011000 5o02yu with 25 (chnou (OovuvuTOvnia donooovno) MNa)2MoA Adogenf 464 (3,0) None 1.1 (4,2) 200 o VI ini V o PI PON o Below are the characteristics of samples of antifriction additives based on surface-modified molybdenum trisulfide nanoparticles obtained in examples 1-23.

Pn b5 o-4 22.0 1.38 12.8 28A vv yav 11111519 83 vva 000000»00000111000960196 vva 60010981 vv o i yuyu 10000066

Triboscopic properties of the obtained nanoparticles

The tribological properties of the obtained antifriction additives based on surface-modified molybdenum trisulfide nanoparticles were studied for their compositions in T46 turbine lubricant using a ZKM vibrotribometer (Oriitoi company, Germany). Test conditions: ball-plane friction couple; amplitude of Ge oscillation mm, frequency 50 Hz; the axial load changes from 20 to 6бО0ОН stepwise, according to their each platform, with a step of 5OH. The value of the coefficient of friction is measured, the test is considered complete if the value of the coefficient of friction exceeds 0.22, or if burr occurs (automatic stop). Lubricant compositions were prepared by mixing 146 with 59 oz. samples 0-1 - 0-23. Surface-modified nanoparticles of molybdenum trisulfide, 4 harvested according to |7| (sample (Mo5,)), and also molybdenum dithiocarbamate of formula III. sch vo-SeNIh, chi 00 ivnsiny Kk

M Mob 0th autumn OOS87D I 00 autumn about her d)

Tribological test data for some samples are shown below. " so what - 64111111 61111781 nem z 60011116 vav vyu zem 00000000000690000000001000090600000100006ю0

Fo (ав) Thus, the proposed method makes it possible to obtain an antifriction additive based on surface-modified nanoparticles of molybdenum trisulfide, which forms transparent, stable dispersions in hydrocarbons and petroleum lubricants, as well as those that effectively reduce the coefficient of friction between metal ka 50 surfaces and increase the critical load. The entire production process can be carried out in one vessel without . intermediate stages of separation and/or purification, without involving large amounts of organic solvents. and Sources of information taken into account: 1. Pat. US Mo4,400,282 (23.08.1983). 2. Pat. US MoMma 4,474,673 (October 2, 1984). 99 3. Pat. USA Mo4,765,918 (23.08.1988).

GF) 4. Pat. USA Mob, 117,826 (September 12, 2000). Yuyu 5. Pat. US Mob, 245,725 (June 12, 2001). 6. Pat. Great Britain Mo2 359 092 (15.08.2001). o 7. Application for US patent UMO 01/94504 A?2 (13.12.2001). b5 and pk t is ko 4 oz i

And and what ka what rime ma o - .

Fig. 1 The electronic splitting spectrum is modified by the addition of particles of mothiiden trisulfide in chloroform "E0a 25 -sh

In 1294 "in with VE-1O - that web i sch zho Emo o and zob in 20 40 bo 80 100 m

Radius, A t s

Fig. 2 Size distribution of modified molybdenum trisulfide nanoparticles (data 5АХ5, solution in tetrahydrofuran) by g)

Claims (6)

The formula of the invention 1. The method of obtaining chemically modified nanoparticles of molybdenum trisulfide and/or its derivatives, suitable for use in lubricant additives, which is characterized by the fact that the nanoparticles of molybdenum trisulfide and/or its derivatives are obtained from salts of thiomolybdic acid of the general formula МоМо5 ;uO,, where M is MH, Ma, x-0-3, in the presence of two modifiers, of which tetraalkylammonium salts or mixtures of salts of the general formula B'B2BZB"MU are used as the first "», where B", 2, BZ and B - " are the same or different, choose from C4-C.v alkyls, X - SI, Bg, and as the second - derivatives of succinimide of the general formula iv, so I M--e («c) o -I where B? - normal or branched alkyl or oligoalkylene with a molecular weight from 140 to about 1000, KE? are selected from the group: Н, -С(О)МН», «СНоСНоМН)СНа, п - 1-4, and the process is carried out by thermal treatment of a mixture of thiomolybdic acid salt and the first modifier homogenized in a polar solvent, cooling the resulting mixture and the following adding a second modifier. 2. The method according to claim 1, which differs in that the heat treatment is carried out at a temperature of 150-220 °C for 1-2 hours. o C. The method according to claim 1, which differs in that methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol or acetone are used as a solvent. name) 4. The method of obtaining chemically modified nanoparticles of molybdenum trisulfide and/or its derivatives, suitable for use in lubricant additives, which is characterized by the fact that 60 nanoparticles of molybdenum trisulfide and/or its derivatives are obtained from molybdenum acid salts of the formula MoMoO,), where M is MH), Ma, and the sulfur donor, as such, an inorganic sulfide or polysulfide of the general formula MiezZy is used, where M' is MH, A, Ma, n - I-4, or thiourea, in the presence of two modifiers, with which are used as the first tetraalkylammonium salts or mixtures of salts of the general formula В'В2ВЗВМХ, where В", 2, ВЗ its в - are the same or different, are chosen from C.-C.v alkyls, X - SI, Vg, and as the second - derivatives succinimide b of the general formula c) , and M--e o where 2? - normal or branched alkyl or oligoalkylene with a molecular weight from 140 to approximately 1000, E9 is selected from the group: Н, -С(-О)МН», "СНоСНоМН ) CH, n-1-4, and the process is carried out by heat treatment of homogenized in polar in the same solvent or benzene mixture of a salt of molybdic acid, a sulfur donor and the first modifier, cooling the resulting mixture and the subsequent addition of the second modifier. 5. The method according to claim 4, which differs in that the heat treatment is carried out at a temperature of 150-220 °C for 1-2 hours. 6. The method according to claim 4, which differs in that methanol, ethanol, propanol, 75 isopropanol, n-butanol, isobutanol, sec-butanol, acetone or benzene are used as a solvent. Official Bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2007, M 17, 25.10.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. c) d) - with . and? (ee) («c) -I of 50 that F) has) 60 b5