RU2249595C1 - Method for production of o-(n-butyl)-o-(3,4,5-trithiatricyclo[5.2.1.02,6]-dez-8-yl-methyl)-dithiophosphoric acid 1-(n,n-dimethylaminomethyl)-1,2,4-triazole salt as lubricant oil additive - Google Patents

Abstract

FIELD: synthesis of lubricant oil additives.

SUBSTANCE: method for production of O-(n-butyl)-O-3,4,5-trithiatricyclo

-dez-8-yl-methyl)-dithiophosphoric acid 1-(N,N-dimethylaminomethyl)-1,2,4-triazole salt of general formula

is disclosed. 1-(N,N-dimethylaminomethyl)-1,2,4-triazole is brought into reaction with equimolar amount of O-(n-butyl)-O-3,4,5-trithiatricyclo

-dez-8-yl-methyl)-dithiophosphoric acid in toluene medium at 80-100°C for 2-4 h.

EFFECT: ash-free antiscoring lubricant oil additive operating under high pressure.

2 tbl, 1 ex

Description

The present invention relates to the field of synthesis of additives for lubricating oils, in particular to a method for producing 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (3,4,5 -trityatricyclo [5.2.1.0 ^2,6 ] dec-8-ylmethyl) -dithiophosphoric acid of the general formula (1), promising as an ashless oil additive.

The specified compound of formula (1) may find application as an additive with enhanced extreme pressure, antiwear properties, high thermal and oxidative stability.

The known method [Pat. US No. 4519928, CL From 10 M 1/32, 1985] the preparation of additives for lubricating oils of the general formula (2) by the alkylation of benzotriazoles. The additive is introduced in an amount of 1 wt.% In the composition of lubricants to give them antioxidant and anticorrosive properties.

where R is hydrogen or a C ₁ -C ₁₂ hydrocarbon radical, R ¹ and R ² are C ₁ -C ₄ alkyl, R ³ is C ₁ -C ₁₂ alkyl.

In a known manner, 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2.6 ] cannot be obtained dec-8-ylmethyl) dithiophosphoric acid (1).

The known method [A.M. Kuliev “Chemistry and technology of additives to oils and fuels”. M., “Chemistry, 1985, p. 312] for obtaining the ash additive DF-11 (zinc salt of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid) of the general formula (3) by reaction pentasulfur phosphorus with isobutyl and isooctyl alcohols at 100-120 ° C to dialkyldithiophosphoric acids, which are neutralized at 20 ° C with zinc oxide.

The known method does not allow to obtain 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2,6 ] dec -8-ylmethyl) -dithiophosphoric acid (1). In addition, the ash additive DF-11 obtained in this way has good antiwear and antioxidant properties, but insufficient anti-seize properties.

The purpose of the invention is the creation of a method for producing ashless additives for lubricating oils operating at high pressures, in particular, additives for oils with improved extreme pressure properties.

The essence of the method is the interaction of equimolar amounts of 1- (N, N-dimethylaminomethyl) -1,2,4-triazole with O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2.6 ] dec-8-ylmethyl) dithiophosphoric acid at a temperature of 80-100 ° C, preferably 90 ° C for 2-4 hours, preferably 3 hours. 1- (N, N-dimethylaminomethyl) -1,2,4-triazole is formed salt of O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2,6 ] dec-8-ylmethyl) dithiophosphoric acid (1) with a yield of 93-100%.

The target product (1) is formed only with the participation of aminomethylated 1,2,4-triazole and O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2,6 ] dec-8-ylmethyl ) dithiophosphoric acid. In the presence of other aminomethylated products (e.g. aminomethylated phenol or 1,2,4-triazole), other dithiophosphoric acid derivatives (e.g. diaryldithiophosphoric acid), the desired product (1) is not formed. Changing the ratio of the starting reagents in the direction of increasing or decreasing one of the components reduces the yield of the target product (1). Reactions were carried out using toluene as a solvent. In other solvents (e.g., aliphatic), the yield of the target product (1) is reduced.

The proposed method has the following advantages.

1. The method allows to obtain in high yields an ashless additive to lubricating oils of the general formula (1), the synthesis of which is not described in the literature.

The method is illustrated by the following examples.

EXAMPLE 1. In a temperature-controlled glass reactor equipped with a mechanical stirrer, a reflux condenser and a gas supply pipe, 100 mmol of 1- (N, N-dimethylaminomethyl) -1,2,4- is placed at room temperature (20-21 ° C) in a nitrogen atmosphere. triazole and 100 mmol of O- (n-butyl) -O- (3,4,5-trithiatricyclo [5.2.1.0 ^2,6 ] dec-8-ylmethyl) dithiophosphoric acid in 30 ml of toluene, heated to 90 ° C with stirring and incubated for 3 hours, 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2.6 ] is isolated dec-8-ylmethyl) dithiophosphoric acid (1) in 96% yield.

Spectral characteristics of 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2,6 ] dec-8- ilmethyl) dithiophosphoric acid (I):

IR (ν, cm ^-1 ): 568 (P = S), 670 (P = S), 740, 952 (P-O), 998 (P-O-C), 1158 (P-O), 1245 (C-O), 2850, 2945. ¹ H NMR (δ, ppm, CDCl _3, TMS): 0.98 (t, 3H, CH _3), 1.32 (m, 4H, with C ^2, C ³ ), 2.72-2.84 (s, 6H at C ¹³ , C ¹⁴ ), 3.30-4.22 (m, 6H, CH ₂ O, CH ₂ S), 5.55 (s, 2H, NCH ₂ N), 8.48, 8.02 ( m, 2H, CH = N). ¹³ C NMR spectrum (δ, ppm): 14.02 (C ¹ ), 19.14 (C ² ), 34.27 (C ³ ), 68.72 (C ⁴ ) 69.17 (C ⁵ ), 40.72 (C ⁶ ), 42.37 ( C ⁷ ), 63.22 (C ⁸ ), 68.76 (C ⁹ ), 41.12 (C ¹⁰ ), 33.49 (C ¹¹ ), 30.68 (C ¹² ), 41.64 (C ¹³ , C ¹⁴ ), 71.27 (C ¹⁵ ), 143.51 (C ¹⁶ ), 151.16 (C ¹⁷ ). Found,%: C, 41.17; H, 6.17; S, 31.92; N, 9.98. C ₂₁ H ₃₁ S ₅ PN ₄ O ₂ . Calculated,%: C, 39.69; H, 6.03; S, 31.13; P, 6.03; N, 10.89; Oh, 6.23.

Other examples confirming the method are given in table 1.

Table 1 No. p / p Reaction temperature, ° C Reaction time, hour Yield (1),% 1 90 3 96 2 100 3 100 3 80 3 93 4 90 4 100 5 90 2 95

The reactions were carried out at an equimolar ratio of the starting reagents in a toluene solution.

Additive (1), obtained according to examples 1-5, was dissolved in industrial oil I-100A in an amount of 3 wt.% And its properties were compared with the known additive DF-11 (Table 2).

table 2
The test results of the additive (1) compared with the known additive DF-11 Indicator Industrial oil I-100A, ν ₅₀ = 100 cSt with 3% wt. additives Additive (1) DF-1 Extreme pressure properties are determined according to GOST 9490-75 on a four-ball friction machine (ChShM). Destructive load, kgf / cm ² 1273 741 Welding load, kgf 315 220 Antioxidant properties (72 hours at 120 ° C with a supply of 5 l of air per hour, copper sheet), method TGL 17745. 3.9 4.5 Centrifuged pellet. 0.1 0.1 Anticorrosion properties in accordance with GOST 2917-76. is absent is absent

As follows from table 2, obtained in accordance with the invention 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2 .1.0 ^2,6 ] dec-8-ylmethyl) dithiophosphoric acid, in comparison with the known additive DF-11 (zinc salt of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid) has better extreme pressure properties, good compatibility with base oil. In addition, they retain the performance properties of the DF-11 additive, such as antioxidant and anticorrosion additives, and therefore are suitable additives for the production of gear oils of the TM-5 class in accordance with TGL 21160. The DF-11 additive allows gearbox oils to be obtained up to the performance class TM- 3.

Claims (1)

The method of obtaining 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2,6 ] dec-8- ilmethyl) dithiophosphoric acid of the formula

as an additive to lubricating oils, 1- (N, N-dimethylaminomethyl) -1,2,4-triazole interacts with an equimolar amount of O- (n-butyl) -O- (3,4,5-tritiatricyclo [5.2.1.0 ^2,6 ] dec-8-ylmethyl) dithiophosphoric acid in toluene at a temperature of 80-100 ° C for 2-4 hours