RU2251547C1 - Method for production of o-(n-butyl)-o-(2-ethyl-n-hexyl)-dithiophosphoric acid 1-(n,n-dimethylaminomethyl)-1,2,4-triazol salt - Google Patents

Abstract

FIELD: new lubricant oiliness addend.

SUBSTANCE: claimed method includes reaction of equimolar amounts of 1-(N,N-dimethylaminomethyl)-1,2,4-triazol and O-(n-butyl)-O-(2-ethyl-n-hexyl)-dithiophosphoric acid at 80-100°C in toluene medium for 2-4 h to produce target product with yield of 94-100 %.

EFFECT: addend compatible with base oil with improved antiscoring properties.

1 cl, 1 ex, 2 tbl

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- (2-ethyl- n-hexyl) -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. USA 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 hydrocarbon C ₁ -C ₁₂ radical, R ¹ - and R ² is 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- (2-ethyl-n-hexyl) dithiophosphoric acid (1) cannot be obtained.

The known method [A.M. Kuliev “Chemistry and technology of additives to oils and fuels”. M., “Chemistry, 1985, p. 312] to obtain the ash additive DF-11 (zinc salt of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid) of the general formula (3), the interaction of five-sulfur 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- (2-ethyl-n-hexyl) 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 consists in the interaction of equimolar amounts of 1- (N, N-dimethylaminomethyl) -1,2,4-triazole with O- (n-butyl) -O- (2-ethyl-n-hexyl) 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 salt of O- (n-butyl) -O- (2 ethyl-n-hexyl) dithiophosphoric acid (1) in a yield of 94-100%.

The target product (1) is formed only with the participation of aminomethylated 1,2,4-triazole and O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid. In the presence of other aminomethylated products (e.g. aminomethylated phenol or benzotriazole), 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, reflux condenser and gas supply tube at room temperature (20-21 ° C), 100 mmol of 1- (N, N-dimethylaminomethyl) -1,2,4-triazole are placed in a nitrogen atmosphere. and 100 mmol of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid in 30 ml of toluene, with stirring, heated to 90 ° C and held for 3 hours, 1- (N, N-dimethylaminomethyl) was isolated ) -1,2,4-triazole salt of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid (1) in 98% yield.

Spectral characteristics of 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid (1):

IR (ν, cm ^-1 ): 565 (P = S), 670 (P = S), 730, 805, 830, 940 (P-O), 1000 (P-O-C), 1120 (P -O), 1200 (C-O), 1270, 1460, 1510, 2860, 2930, 2940, 3100 (NH). ¹ H NMR spectrum (δ, ppm, CDCl ₃ , TMS): 0.89, 0.96 (m, 9H, 3H), 1.29 (m, 12H, CH ₂ ), 1.86-2.03 (m, 1H, CH) 2.70, 2.82 (s, 6H, CH ₃ ), 3.67-3.95 (m, 4H, CH ₂ O), 5.69 (s, 2H, NCH ₂ N), 8.00, 8.51 (s, 2H, CH = N). ¹³ C NMR spectrum (δ, ppm): 14.09 (C ¹ ), 19.08 (C ² ), 35.06 (C ³ ), 68.64 d (C ⁴ , ² J _sr = 8.8 Hz), 14.09 (C ⁵ ) 23.00 (C ⁶ ), 28.85 (C ⁷ ), 30.02 (C ⁸ ), 39.83 (C ⁹ , ³ J _pc = 8.8 Hz), 72.54 (C ¹⁰ , ² J _pc = 8.8 Hz), 23.32 (C ¹¹ ) 10.90 (С ¹² ), 41.59 (С ¹³ , С ¹⁴ ), 71.35 (С ¹⁵ ), 143.37 (С ¹⁶ ), 151.50 (С ¹⁷ ). Found,%: C, 49.70; H, 9.09; S, 15.69; N, 13.08. C ₁₇ H ₃₇ S ₂ PN ₄ O ₂ . Calculated,%: C, 48.11; H, 8.73; S, September 15; P, 7.31; N, 13.21; Oh, 7.55.

Other examples confirming the method are given in table 1.

Table 1 No. p / p The reaction temperature, ° C Reaction time, hour Yield (1),% 1. 90 3 98 2. 100 3 100 3. 80 3 94 4. 90 4 100 5. 90 2 96

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 the table. 2, obtained in accordance with the invention, 1- (N, N-dimethylaminomethyl) -1,2,4-triazole salt of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid has compared to the well-known additive DF-11 (zinc salt of O- (n-butyl) -O- (2-ethyl-n-hexyl) dithiophosphoric acid) 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 anticorrosive additives, as a result, they are suitable additives for producing 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- (2-ethyl-n-hexyl) dithiophosphoric acid of the formula

as an additive to lubricating oils, which consists in the fact that 1- (N, N-dimethylaminomethyl) -1,2,4-triazole interacts with an equimolar amount of O- (n-butyl) -O- (2-ethyl-n- hexyl) dithiophosphoric acid in toluene at a temperature of 80-100 ° C for 2-4 hours