US20060094605A1

US20060094605A1 - Method for producing lubricant additive (variants)

Info

Publication number: US20060094605A1
Application number: US10/532,416
Authority: US
Inventors: Viktor Bakunin; Galina Kuz'mina; Oleg Parenago
Original assignee: Institut Neftekhimicheskogo Sinteza Imeni A V Topchieva
Current assignee: Institut Neftekhimicheskogo Sinteza Imeni A V Topchieva; AV Topchiev Institute of Petrochemical Synthesis
Priority date: 2002-10-23
Filing date: 2003-10-16
Publication date: 2006-05-04
Also published as: EA200500556A1; GB2411660B; UA80727C2; GB2411660A; JP2006503954A; EA008515B1; CN1723269A; GB0510381D0; AU2003277760A1; CN100384969C; RU2002128364A; WO2004037957A1; DE10393575T5

Abstract

The invention relates to petroleum chemistry, more specifically to sulfur-containing molybdenum compounds and to the use thereof in the form of lubricant additives which decrease friction coefficient. In the first variant, molybdenum trisulfide nanoparticles and the derivatives thereof are produced from thio-molybdenum acid salts of the general formula M₂MoS_4-xO_x, wherein M=NH₄, Na, x=0-3 in the presence of two modifiers, one of them being embodied in the form of tetra-alkyl-ammonium salts or a mixture of salt of the general formula R¹R²R³R⁴NX, wherein R¹R²R³and R⁴equal or different are selected from a group containing C₁-C₁₆alkyl, X=Cl, Br, the second modifier being embodied in the form of a succinimide of the general formula Formula wherein R⁵=straight or branched-chain alkyl or oligoalkylene whose molar mass ranges from 140 to about 1000, R⁶is selected from a group comprising H, —C(═O)NH₂, —(CH₂CH₂NH)_nCH₃, n=14. The process is carried out by means of a thermal treatment which is homogenised in the polar solvent of the mixture of a thio-molybdenum acid salt and the first or second modifier, cooling the thus produced-mixture and a subsequently adding the second or the first modifier, respectively. In the second variant, the inventive method consists in producing molybdenum trisulfide nanoparticles and the derivatives thereof from molybdenum acid salts of the formula M₂MoO₄, wherein M=NH₄, Na, and a sulphur donator embodied in the form of an inorganic sulphide or a polysulfide of the general formula M′₂S_n, wherein M′=M=NH₄, Na, n=1-4, or a thiocarbamide, afterwards, the first variant being used.

Description

CROSS-REFERENCE TO RELATED APPLICATION

This Application is a Section 371 National Stage Application of International Application No. PCT/RU2003/00440, filed Oct. 16, 2003 and published as WO 2004/037957 A1 on May 6, 2004, not in English.

FIELD OF THE INVENTION

The present invention relates to the field of petrochemistry, more particularly to molybdenum compounds comprising sulfur and their use as additives in lubricating materials for reducing friction coefficient.

BACKGROUND OF THE INVENTION

It is well-known that in order to reduce fuel consumption and the wear of machine parts during friction, antifriction additives (friction modifiers) are introduced into lubricating oils. It is also known that oil-soluble complex molybdenum are used as the friction modifiers, which compounds include sulfur, nitrogen or phosphor atoms as ligands.
Thus, for example, in US patent [1] a method is described for preparing lubricating oil additives based on tetraalkyl(alkenyl)ammonium thiomolybdate, improving the antifriction properties of the oil. The use of relatively hard-to-obtain and expensive alkyl and alkenyl groups produced from vegetable oils and fats, for example, cacao or soybean oil, as constituents of one of the initial components, and namely a tetraalkylammonium halogenide, relates to drawbacks of the proposed method.
A method is known [2] in which additives to lubricating oils are prepared by reacting a sulfur-comprising organic compound, having an active hydrogen atom, with molybdenum pentachloride. The product isolated as a result of the reaction contains 3% of molybdenum and about 1% of chlorine, which is undesirable for ecological reasons and because of the possible corrosive activity of the product.
A molybdenum-comprising additive to lubricating oils, which exhibits antifriction and antioxidation properties, is prepared as described in US patent [3], in three steps, wherein in the first step a reaction is carried out of a triglyceride of vegetable oil with a nitrogen-comprising compound, then in the second step the product of the first step is reacted with a molybdenum compound, and in the third step the product of the second step is reacted with sulfur or a sulfur-containing compound. The relatively complex manner of synthesis (multi-stage process, the presence of an inert atmosphere, rigid limitation of the temperature ranges) should be considered as drawbacks of the method.
Methods [4,5] are known, where oil additives based on dithiocarbamyl complexes of molybdenum are prepared. These additives are polyfunctional (including antifriction properties), but their synthesis is very complex and involves the use of toxic reagents, e.g., carbon disulfide.
A method is known, in accordance with which an additive to oils is prepared based on a mixture of a friction modifier (nitrogen- or oxygen-comprising organic compound) and a trinuclear sulfur-containing molybdenum complex comprising dithiocarbamine groups as the ligands [6]. The complex makeup of the additive and the multi-stage synthesis of the organomolybdenum compound are disadvantages of the method.
The most similar analog of the claimed invention is the method [7], in which an antifriction additive is prepared in the form of chemically modified nanosized particles of molybdenum trisulfide. In this method, the nanosized particles of molybdenum trisulfide are prepared by forming inverted microemulsions of the “water-in-oil” type, stabilized by surfactants, and comprising water-soluble salts of molybdic acid in an aqueous phase, converting them into salts of thiomolybdic acid by reacting with hydrogen sulfide and subsequent isolation of nanosized particles of MoS₃, preliminarily processed with modifying compounds. As a result, nanosized particles of molybdenum trisulfide are obtained, which are stable in hydrocarbon media, including oils, and which exhibit high effectiveness as antifriction additives. The low technological effectiveness of synthesis of the additive, which is related to carrying out the process in strongly diluted organic solutions and to the use of hydrogen sulfide as the reagent, should be considered as drawbacks of this method.
The object of the proposed invention is to provide a convenient and technological method of preparing an additive for lubricating materials based on chemically modified nanosized particles of molybdenum trisulfide and derivatives thereof.

SUMMARY OF THE INVENTION

In order to realize the stated object, the instant method of preparing additives for lubricating materials is provided, with two embodiments realizing said method being proposed.
In accordance with the first embodiment, a method of preparing additives for lubricating materials based on chemically modified nanosized particles of molybdenum trisulfide and/or derivatives thereof comprises preparing the nanosized particles of molybdenum trisulfide and/or derivatives thereof from salts of thiomolybdic acid of the general formula M₂MoS_4-xO_x, where M is NH₄, Na, x is 0-3, in the presence of two modifiers, where tetraalkylammonium salts of the general formula R¹R²R³R⁴NX, wherein R¹, R², R³and R⁴are identical or different and are independently selected from the group consisting of C₁-C₁₆alkyl, X is Cl or Br, or mixtures thereof are used as the first modifier, while derivatives of succinimide of the general formula

where R⁵is normal or branched alkyl or oligoalkylene with a molecular weight of from 140 to about 1000, R⁶is selected from the group consisting of H, —C(═O)NH₂, —(CH₂CN₂NH)_nCH₃, n is 1 to 4, are used as the second modifier,
wherein said process is carried out by thermally processing a homogenized in a polar solvent mixture of said salt of thiomolybdic acid and said first or second modifier, cooling the obtained mixture and subsequently adding said second or first modifier, respectively.
The second embodiment of realizing the method according to the present invention consists in that the nanosized particles of molybdenum trisulfide and/or derivatives thereof are prepared from salts of molybdic acid of the general formula M₂MoO₄where M is NH₄, Na, and a sulfur donor which is an inorganic sulfide or polysulfide of the general formula M′₂Sn, wherein M′ is NH₄, Na, n is 1 to 4, or thiourea, in the presence of two modifiers, modifiers, where tetraalkylammonium salts of the general formula R¹R²R³R⁴NX, wherein R¹, R², R³and R⁴are identical or different and are independently selected from the group consisting of C₁-C₁₆alkyl, X is Cl or Br, or mixtures thereof are used as the first modifier, while derivatives of succinimide of the general formula

where R⁵is normal or branched alkyl or oligoalkylene with a molecular weight of from 140 to about 1000, R⁶is selected from the group consisting of H, —C(═O)NH₂, —(CH₂CN₂NH)_nCH₃, n is 1 to 4, are used as the second modifier,
wherein the process is carried out by thermally processing a homogenized in a polar solvent mixture of said salt of molybdic acid, said sulfur donor, for which an inorganic sulfide, polysulfide or thiourea is used, and said first or second modifier, cooling the obtained mixture and subsequently adding said second or first modifier, respectively.
In the proposed method, in accordance with any of the above embodiments, the thermal processing is carried out at a temperature of 150 to 220° C. for 1 to 2 hours, while methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, 2-butanol, acetone or benzene is used as the solvent.
Tetraalkylammonium salt is selected from the group consisting of tricapryl-methylammonium chloride (Alikvat® 336), methyl-trialkyl(C₈-C₁₀)ammonium chloride (Adogen® 464), cetyl-trimethylammonium bromide (CTAB).
The product prepared by any variant of carrying out the method is filtered in order to isolate the solid admixtures and to remove the residues of volatile organic solvents under vacuum. The whole process of preparation may be carried out in one pot, without intermediate steps of isolating and/or purifying, without involving large amounts of organic solvents.
The prepared product is a viscous liquid of dark brown color, easily miscible with hydrocarbons and petroleum oils to form transparent solutions or compositions, which have a color from reddish-brown to brown. The content of molybdenum in the product is usually from 0.5 to 2.0% by weight. Solutions of the obtained product are stable dispersions of surface-modified nanosized particles of molybdenum trisulfide, which is confirmed by data of electronic spectroscopy in the UV and visual region (FIG. 1) and a small-angle X-ray spread (SAXS) (FIG. 2). The SAXS method makes it possible to determine the dimensions of the inorganic core of the nanosized particles, which are within the range of from 1 to 6 nm and, as different from the surface-modified nanosized particles described in [7], are characterized by monodisperse size distribution. The latter circumstance makes it possible to presume a higher degree of reproducibility of the synthesis.
The examples below illustrate the instant invention, but do not in any manner limit the scope thereof in any way.

EXAMPLE 1

A homogeneous mixture prepared by mixing at 60° C. 0.12 g of ammonium tetrathiomolybdate, 3.0 g of methyltrialkyl(C₈-C₁₀)ammonium chloride (Adogen® 464) and 5 ml of methanol is subjected to thermal processing at 200° C. for 2 hours, the product residue is 30% of the total starting weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered through a “blue belt” filter, the solvent is removed under vacuum. The content of molybdenum in the product is 1.22%. There are no absorption bands corresponding to ammonium tetrathiomolybdate in the UV spectrum of the prepared product.

EXAMPLE 2

A homogeneous mixture prepared by mixing at 60° C. 0.12 g of ammonium tetrathiomolybdate, 3.0 g of tricaprylmethylammonium chloride (Alikvat® 336) and 5 ml of methanol is subjected to thermal processing at 200° C. for 2 hours, the product residue o is 29% of the total starting weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered as in Example 1, the solvent is removed under vacuum. The content of molybdenum in the product is 1.25%.

EXAMPLE 3

A homogeneous mixture prepared by mixing at 60° C. 0.12 g of ammonium tetrathiomolybdate, 3.0 g of cetyltrimethylammonium bromide (CTAB) and 10 ml of a methanol-chloroform 1:1 mixture is subjected to thermal processing at 200° C. for 2 hours, the residue of the product is 55% of the total original weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.36%.

EXAMPLE 4

A homogeneous mixture prepared by mixing at 60° C. 0.12 g of ammonium tetrathiomolybdate, 1.5 g of CTAB and 1.5 g of Adogen® and 10 ml of a methanol-chloroform 1:1 mixture is subjected to thermal processing at 200° C. for 2 hours, the product residue is 42% of the total starting weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.38%.

EXAMPLE 5

A homogeneous mixture prepared by mixing at 60° C. 0.12 g of ammonium tetrathiomolybdate, 3.0 g of Adogen® and 5 ml of methanol is subjected to thermal processing at 180° C. for 2 hours, the product residue is 29% of the starting weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.19%.

EXAMPLE 6

A homogeneous mixture prepared by mixing at 60° C. 0.12 g of ammonium tetrathiomolybdate, 3.0 g of Adogen® and 5 ml of methanol is subjected to thermal processing at 210° C. for 2 hours, the product residue is 27.5% of the starting weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.25%.

EXAMPLE 7

A homogeneous mixture prepared by mixing at 60° C. 0.24 g of ammonium tetrathiomolybdate, 3.0 g of Adogen® and 5 ml of acetone is subjected to thermal processing at 200° C. for 2 hours, the product residue is 26.2% of the starting weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 2.92%.

EXAMPLE 8

A homogeneous mixture prepared by mixing at 60° C. 0.12 g of ammonium tetrathiomolybdate, 3.0 g of Adogen® and 5 ml of methanol is subjected to thermal processing at 200° C. for 2 hours, the product residue is 28.2% of the starting weight of the components. 4.2 g of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, the solvent is removed under vacuum. The content of molybdenum in the product is 1.22%.

EXAMPLE 9

A homogeneous mixture prepared by mixing at 60° C. 0.24 g of ammonium tetrathiomolybdate, 3.0 g of Adogen® and 5 ml of methanol is subjected to thermal processing at 200° C. for 2 hours, the product residue is 30.1% of the original total weight of the components. 4.2 g of an N-alkylenamino derivative of alkenylsuccinimide and 5 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, the solvent is removed under. The content of molybdenum in the product is 1.19%.

EXAMPLE 10

The method of preparing according to Example 1, except for that ethanol is used instead of methanol.

EXAMPLE 11

The method of preparing according to Example 1, except for that propanol is used instead of methanol.

EXAMPLE 12

The method of preparing according to Example 1, except for that isopropanol is used instead of methanol.

EXAMPLE 13

The method of preparing according to Example 1, except for that n-butanol is used instead of methanol.

EXAMPLE 14

The method of preparing according to Example 1, except for that iso-butanol is used instead of methanol.

EXAMPLE 15

The method of preparing according to Example 1, except for that 2-butanol is used instead of methanol.

EXAMPLE 16

The method of preparing according to Example 9, except for that ammonium trithiomolybdate is used instead of ammonium tetrathiomolybdate.

EXAMPLE 17

The method of preparing according to Example 9, except for that ammonium dithiomolybdate is used instead of ammonium tetrathiomolybdate.

EXAMPLE 18

The method of preparing according to Example 9, except for that ammonium monothiomolybdate is used instead of ammonium tetrathiomolybdate.

EXAMPLE 19

A homogeneous mixture prepared by mixing at 60° C. 0.0095 g of ammonium molybdate, 0.0113 g of Na₂S-9H₂O and 0.0360 g of Adogen® in 1 ml of benzene is subjected to thermal processing at 200° C. for 30 minutes. The product residue after thermal processing is 48% of the total weight of the starting components. 0.0420 g of alkenylsuccinimide and 1 ml of chloroform are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered through a “blue belt” filter, then the solvent is removed under vacuum. The content of molybdenum in the product is 1.35%.

EXAMPLE 20

The method of preparing according to Example 1, wherein at first 0.12 g of ammonium tetrathiomolybdate and 4.2 g of alkenylsuccinimide are homogenized, the mixture is subjected to thermal processing at 180-200° C. for 1 hour, then 3.0 g of Adogen® are added to the residue, homogenized and subjected to thermal processing at 180-200° C. during 1 hour. The residue is dissolved in chloroform, filtered, the solvent is removed under vacuum. As a result, a product is obtained with a molybdenum content of 0.66%.

EXAMPLE 21

A homogeneous mixture prepared by mixing at 60° C. 0.0102 g of ammonium molybdate, 0.0320 g of Adogen®, 0.0101 g of thiourea and 5 ml of benzene is subjected to thermal processing at 200° C. for 2 hours. The product residue after thermal processing is 43.0% of the total weight of the starting components. 5 ml of chloroform and 0.042 g of alkenylsuccinimide are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, then the solvent is evaporated under vacuum. The content of molybdenum in the product is 2.35%.

EXAMPLE 22

A homogeneous mixture prepared by mixing at 60° C. 0.0101 g of ammonium molybdate, 0.0315 g of Adogen®, 0.0145 g of Na₂S₂O₃0.5H₂O and 5 ml of benzene is subjected to thermal processing at 200° C. for 2 hours. The product residue after thermal processing is 39.0% of the total weight of the starting components. 5 ml of chloroform and 0.042 g of alkenylsuccinimide are added to the product residue, the mixture is stirred with a magnetic stirrer, filtered, and then the solvent is evaporated under vacuum. The content of molybdenum in the product is 1.31%.
All the results are presented in Table 1.

The characteristics of samples of antifriction additives based on surface-modified nanosized particles of molybdenum trisulfide as prepared in Examples 1-22 are presented below.



		Concentration of	Ratio	Average size
		molybdenum,	Mo:S,	of particles,
Sample No.	Yield, wt. %	wt. %	mole/mole	angstrom

O-1	26.1	1.22	1:2.5	27.3
O-2	31.3	1.25	1:2.7	32.4
O-3	20.3	1.36	1:3.1	28.1
O-4	22.0	1.38	1:2.8	28.4
O-5	22.4	1.19	1:2.9	26.7
O-6	27.5	1.25	1:2.7	33.3
O-7	33.8	2.92	1:2.9	30.5
O-8	31.2	1.22	1:2.6	29.0
O-9	35.9	1.19	1:2.5	29.6
O-10	37.4	1.08	1:3.2	28.9
O-11	27.6	1.32	1:2.7	29.4
O-12	21.1	1.40	1:2.7	27.9
O-13	25.8	1.11	1:2.5	26.9
O-14	19.7	2.03	1:2.8	26.8
O-15	26.1	1.56	1:2.1	24.7
O-16	22.6	1.34	1:1.8	31.4
O-17	35.2	0.98	1:1.1	34.3
O-18	20.3	2.56	1:2.3	28.1
O-19	15.9	1.35	1:2.6	28.2
O-20	30.5	0.66	1:2.7	27.2
O-21	27.0	2.35	1:3.0	26.7
O-22	20.6	1.31	1:3.1	29.6

Tribological Properties of Prepared Nanosized Particles
The tribological properties of the prepared antifriction additives based on surface-modified nanosized particles of molybdenum trisulfide were studied with respect to their composition in turbine oil T46 with the use of a vibrating tribometer SRV (Optimol firm, Germany). Test conditions: friction pair—ball-plane; amplitude of oscillations—1 mm, frequency 50 Hz; axial load changes from 20 to 600 N step-by-step, 1 min at each step, the step being 50 N. The value of the coefficient of friction is measured, the test is considered to be finished in the case where the value of the coefficient of friction exceeds 0.22, or if there is a scratch (automatic stop). The oil compositions were prepared by mixing T46 with a 5 wt. % of samples 0-1 to 0-22. Surface-modified nanosized particles of molybdenum trisulfide, prepared in accordance with [7] (sample [MoS_x]) and also molybdenum dithiocarbamate of formula III are used as a sample for comparison.
Data on tribologic tests conducted in respect to some samples are shown below.

Amount of Mo in Minimum

oil, parts coefficient Critical

Sample No. per million of friction load, N

O-1 670 0.065 No

O-2 625 0.065 No

O-4 690 0.065 No

O-19 675 0.066 600

O-21 1175 0.060 No

sample [MoS_x] 650 0.065 600

Mo(III) dithiocarbamate 1000 0.067 550
Thus, the proposed method makes it possible to prepare an antifriction additive on the basis of surface-modified nanosized particles of molybdenum trisulfide, this additive forming transparent, stable dispersions in hydrocarbons and petroleum oils, and also effectively reducing the coefficient of friction between the metal surfaces and increasing the critical load. The whole process may be carried out in one pot without intermediate steps of isolating and/or purifying, without involving large amounts of organic solvents.
Sources of information, taken into account:

- 1. U.S. Pat. No. 4,400,282 (23 Aug. 1983)
- 2. U.S. Pat. No. 4,474,673 (2 Oct. 1984)
- 3. U.S. Pat. No. 4,765,918 (23 Aug. 1988)
- 4. U.S. Pat. No. 6,117,826 (12 Sep. 2000)
- 5. U.S. Pat. No. 6,245,725 (12 Jun. 2001)
- 6. Great Britain Patent No. 2 359 092 (15 Aug. 2001)

7. US Patent application WO 01/94504 A2 (13 Dec. 2001)

TABLE 1


		Salt of quartenary		Derivative of	Temperature of
Example	Salt of thiomolybdic acid	ammonium base	Inorganic sulfide	succinimide	synthesis

No.	(amount, g)/solvent	(amount, g)	(amount, g)	(amount, g)	Step 1, ° C.	Step 2, ° C.

1	(NH₄)₂MoS₄(0.12)/no	Adogen ® 464 (3.0)	No	II.1 (4.2)	60	200
2	(NH₄)₂MoS₄(0.12)/methanol	Alikvat ® 336 (3.0)	No	II.1 (4.2)	60	200
3	(NH₄)₂MoS₄(0.12)/methanol	CTAB (3.0)	No	II.1 (4.2)	60	200
4	(NH₄)₂MoS₄(0.12)/methanol	CTAB: Adogen 1:1 (3.0)	No	II.1 (4.2)	60	200
5	(NH₄)₂MoS₄(0.12)/methanol	Adogen (3.0)	No	II.1 (4.2)	60	180
6	(NH₄)₂MoS₄(0.12)/methanol	Adogen (3.0)	No	II.1 (4.2)	60	210
7	(NH₄)₂MoS₄(0.24)/methanol	Adogen (3.0)	No	II.1 (4.2)	60	200
8	(NH₄)₂MoS₄(0.12)/methanol	Adogen (3.0)	No	II.2 (4.2)	60	200
9	(NH₄)₂MoS₄(0.12)/methanol	Adogen (3.0)	No	II.3 (4.2)	60	200
10	(NH₄)₂MoS₄(0.12)/ethanol	Adogen (3.0)	No	II.1 (4.2)	60	200
11	(NH₄)₂MoS₄(0.12)/propanol	Adogen (3.0)	No	II.1 (4.2)	60	200
12	(NH₄)₂MoS₄(0.12)/isopropanol	Adogen (3.0)	No	II.1 (4.2)	60	200
13	(NH₄)₂MoS₄(0.12)/n-butanol	Adogen (3.0)	No	II.1 (4.2)	60	200
14	(NH₄)₂MoS₄(0.12)/isobutanol	Adogen (3.0)	No	II.1 (4.2)	60	200
15	(NH₄)₂MoS₄(0.12)/2-butanol	Adogen (3.0)	No	II.1 (4.2)	60	200
16	(NH₄)₂MoOS₃(0.12)/methanol	Adogen (3.0)	No	II.1 (4.2)	60	200
17	(NH₄)₂MoO₂S₂(0.15)/methanol	Adogen (3.0)	No	II.1 (4.2)	60	200
18	(NH₄)₂MoO₃S(0.21)/methanol	Adogen (3.0)	No	II.1 (4.2)	60	200
19	(NH₄)₆Mo₇S₂₄(0.0095)/benzene	Adogen (0.03)	Na₂S (0.0119)	II.1 (0.04)	60	200
20	(NH₄)₂MoS₄(0.12)/methanol	Adogen (3.0)	No	II.1 (4.2)	60	200
21	(NH₄)₆Mo₇O₂₄(0.0095)/benzene	Adogen (0.03)	Thiourea (0.01)	II.1 (0.04)	60	200
22	(NH₄)₆Mo₇O₂₄(0.0095)/benzene	Adogen (0.03)	Na₂S₂O₃5H₂O (0.01)	II.1 (0.04)	60	200

Claims

1. A method of preparing additives for lubricating materials on the basis of chemically modified nanosized particles of molybdenum trisulfide and/or derivatives thereof, characterized in that the nanosized particles of molybdenum trisulfide and/or derivatives thereof are prepared from salts of thiomolybdic acid of the general formula M₂MoS_4-xO_x, where M is NH₄, Na, x is 0-3, in the presence of two modifiers, where tetraalkylammonium salts or mixtures of salts of the general formula R¹R²R³R⁴NX are used as the first modifier, wherein R¹, R², R³and R⁴are identical or different and are selected from the group consisting of C₁-C₁₆alkyl, X is Cl, Br, while derivatives of succinimide of the general formula

are used as the second modifier, wherein R⁵is normal or branched alkyl or oligoalkylene having a molecular weight of from 140 to about 1000, R⁶is selected from the group consisting of H, —C(═O)NH₂, —(CH₂CN₂NH)_nCH₃, n is 1-4,

wherein the process is carried out by thermally processing a homogenized in a polar solvent mixture of said salt of thiomolybdic acid and said first or second modifier, cooling the obtained mixture and subsequently adding said second or first modifier, respectively.

2. A method of preparing additives for lubricating materials on the basis of chemically modified nanosized particles of molybdenum trisulfide and/or derivatives thereof, characterized in that the nanosized particles of molybdenum trisulfide and/or derivatives thereof are prepared from salts of molybdic acid of the general formula M₂MoO₄, where M is NH₄, Na, and a sulfur donor, which is an inorganic sulfide or polysulfide of the general formula M′₂Sn wherein M′ is NH₄, Na, n is 1-4, or thiourea, in the presence of two modifiers, where tetraalkylammonium salts or mixtures of salts of the general formula R¹R²R³R⁴NX are used as the first modifier, wherein R¹, R², R³and R⁴are identical or different and are selected from the group consisting of C₁-C₁₆alkyl, X is Cl, Br, while derivatives of succinimide of the general formula

are used as second modifier where R⁵is normal or branched alkyl or oligoalkylene having a molecular weight of from 140 to about 1000, R⁶is selected from the group consisting of H, —C(═O)NH₂, —(CH₂CN₂NH)_nCH₃, n is 1-4,

wherein the process is carried out by thermally processing a homogenized in a polar solvent mixture of said salt of molybdic acid, said sulfur donor which is an inorganic sulfide, polysulfide or thiourea, and said first and/or second modifier, cooling the obtained mixture and subsequently adding said second and/or first modifier, respectively.

3. The method according to claim 1 characterized in that the thermal processing is carried out at a temperature of 150 to 220° C. for 1-2 hours.

4. The method according to claim 1, characterized in that methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, 2-butanol, acetone or benzene is used as the solvent.

5. The method according to claim 2, characterized in that the thermal processing is carried out at a temperature of 150 to 220° C. for 1-2 hours.

6. The method according to claim 2, characterized in that methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, 2-butanol, acetone or benzene is used as the solvent.