SU1447843A1 - Method of producing high-pressure additives - Google Patents

Abstract

The invention relates to lubricating compositions, in particular, a process for the preparation of dithiophosphate-based additives for high pressure, for example, for high-performance EP oils. The goal is to create a method for producing effective additives. The synthesis of target additives is carried out by the reaction of tritian alcohols of the formula CHjOH with five-grained phosphorus in a medium of dry inert solvent at 60 (preferably at). Or, tritiated alcohols of this formula are reacted with di-C ,, 5-alkyl dithiophosphoric acid in the presence of an aliphatic alcohol at its boiling point in vacuum. The resulting reaction product is treated with C5 2l-alkylamine at 30-100 ° C. As a solvent, it is desirable to use components of mineral oils or aromatic or alkyl aromatic hydrocarbons. New additives can be used to obtain TM-5 gear oils (versus TM-3 in the case of using known additives) 1C. f-ly, 2 tab. i 3SlSS% w

Description

The invention relates to methods for producing additives for high pressure, in particular for high-performance EP oils,

Dithiophosphates are used as anti-wear additives or as antioxidants. Such additives are obtained by the interaction of n-dispersed phosphorus (l mol) with 4 mol alcohols at 100-120 ° C to dialkyldithiophosphoric acids. These acids are oily, viscous, non-crystallizing substances that cannot be distilled without decomposition. Dialkyldithiophosphoric acids are converted into oil-soluble compounds by neutralization and their hydroxides or algae boles BA, Mg, Ca, A1, Zn or Sn, organo- bases or polyethylene amine. The dialkyldithiophosphates thus obtained are good oxidation inhibitors and have anti-seize properties (US Pat. No. 3,813,336, Cl. 252-32.7, 1974),

The purpose of the invention is to create a method for producing additives for high pressure, in particular additives for gear lubricants, at lower cost and with improved extreme pressure (EP) properties.

In accordance with the invention, high-pressure additives are obtained by reacting tritianova alcohols of the general formula

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 With pepticular phosphorus in a dry inert solvent at 60–100 ° C, preferably at 80 ° C, or by reacting trithian alcohols of the above formula with dialkyl dithiophosphoric acid, where alkyl is s in the presence of an aliphatic alcohol at its boiling point in vacuum, followed by processing the obtained reaction product alkylamino Cj-C24 at 30-100 C.

As the solvent, use components of mineral oils, aromatic or alkyl aromatic hydrocarbons. As amines is

ten

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20

25

478432

use primary and / or secondary alkylamines with chain length,

Example 1. In a sulfonation flask equipped with a mechanical stirrer, a reflux condenser and a gas supply tube, 35.4 g of 8-hydroxymethyl-3,4,5-exotitiatricyclo 5,2,1.0 are dissolved in dry benzene (150 ml) J -decane (A), with stirring under a stream of nitrogen, is heated to 80 ° C and mixed in portions with 9.3 g of tetrous phosphate. After 4 hours, the five-grained phosphorus is almost completely dissolved. The precipitate is filtered off and the benzene is removed in vacuo to obtain a solution containing 50 ml of 0.027 mol of di (3,4,5-exotritia tricyclo 5,2, 1, J decane-8-endo-4-1-methoxy) -dithiophosphoric acid ( AT). 50 ml of this solution are mixed with 2.2 g of p-butylamine and heated to reflux. After boiling for 30 minutes, the solvent is completely separated in vacuo. P-butylammonium-di (3,4,5-exotritytricyclo 5,2, 1. -Decan 8-endomethoxy) -dithiophosphate is obtained.

Example 2.50 ml of dithiophosphoric acid benzene solution prepared in accordance with — for example 1 is boiled for 30 minutes with 8 g of a technical mixture of amines G g-0–2.4 in reverse fridge. The solvent is then distilled off in vacuo. A mixture of di (-3, 4,5-exotritytricyclo 5.2, 1.0 J-decane 8-endomethoxy) ammonium dithiophosphates is obtained.

Example 3. In a distillation flask, 27 g of diamyldithiophosphoric acid are mixed with 22 g of compound A and slowly under vacuum (0.3 mmHg, degree) are heated in an oil bath first to 70 ° C and then to 90 ° C, and dispersed amyl alcohol slowly, over 4 hours, is distilled off. 20 g of the resulting amyl- (3,4,5-exotriethri-cyclo, 2,1,0 J -decan-8-endomethoxy) Dithiophosphoric acid (C) is dissolved in 100 ml of dry benzene and heated under reflux for 30 min. from 9.5 g of dodecylamine to boiling. The solvent is then distilled off in vacuo. The dodecylammonium salt of compound C remains.

Example 4. 111.6 g of dodecyl alcohol is reacted with 33.3 33.3 g in 100 ml of dry benzene, turning into diddedyl dithiophosphorus

thirty

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50

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acid (D) and then carried out the separation as described in example 1. 74.6 g of compound D is mixed with 35.3 g of compound A, slowly at a pressure of 0.2 mm Hg, heated in a distillation flask to and 24.2 g of dedecyl alcohol is distilled off within 5 hours. The remaining dode of Cyl- (3,4,5-exotritytricyclo 5.2, 2,1.0 J -decan-8-endomethoxy) -dithiophosphoric acid (E) is emulsified in gasoline. Compound E peels off at the bottom as a viscous mass.

25 g of compound E are dissolved in 200 ml of dry benzene and heated under reflux for 30 minutes to boiling with 9.3 g of dodecylamine. In accordance with Example 1, the solvent is removed and the dodecylammonium salt of compound E is obtained.

Example 5. In accordance with Example 1, the reaction is converted to di- (2-ethylhexyl) -dithiophosphoric acid (F) 52 g of 2-ethylhexanol with 22.2 g in 80 ml of absolute benzene, 44 g of this compound neither is mixed with 27.3 g of compound A and slowly, under a pressure of 2 mm Hg, heated in a distillation flask on an oil bath to 120 ° C. The split 2-ethylhexanol is distilled off within 5 hours. A residue is obtained 2-ethylhexyl- (3,4,5-ectriatritsi-, 2,1. -Decane-8-endomethoxy) - dithiophosphoric acid (G).

10 g of this dithiophosphoric acid are dissolved in 100 ml of benzene dry and, for 30 minutes, boiled under reflux with 4.2 g of dodecylamine. After the solvent is distilled off, the dodecylammonium salt of compound G remains. Example 6. 126 g of didodecyl-dithiophosphoric acid is transesterified with 60 g of compound A, as in Example 4. Compound A is purified by distillation in vacuo at 0.1 mm Hg. up to 100 C.

The cleaved dodecyl alcohol is distilled off.

50 g of the obtained reaction product is suspended in 200 g of G100 basic gear oil and combined with a heated solution of 18.5 g of dodecylamine in 400 g of basic gear oil. A clear, stable oil solution of the dodecylammonium salt of compound E is obtained.

1447843

Example 7. 63.4 g of compound D are suspended in 100 g of the main gearbox oil G100, mixed with

30 g of compound A and slowly under vacuum are heated on an oil bath, the bath temperature reaching a final value of 140 ° C.

For 4 hours with and

0.8 Torr. 20.3 g of dodecyl alcohol are distilled off. Compound E is obtained in the main gear oil. At this time, 24.6 g of dodecylamine are added to this mixture with stirring.

a clear solution of the dodecyl ammonium salt of compound E is obtained.

Compounds of tritiolandithiophosphoric acid obtained in accordance with the invention possess, compared with the known dialkyl dithiophosphates, better anti-seize (EP) and anti-foam properties and good compatibility with other materials of the reducer.

Properties of the additives are given in table.1.

In addition, they retain such performance properties of zinc dialkyldithiophosphates as antioxidants.

lining and anticorrosive, and as a result are suitable additives for high pressures to produce gear oils of the highest performance class

TM 5 in accordance with TGL 21160, as follows from table 2. Known dialkyldithiophosphates make it possible to obtain reducer oils up to the performance class TM 3.

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Claims (2)

1. A method for producing high pressure additives based on dithiophosphate, characterized in that trithian alcohols of the general formula 50 55 / CH.OH and is reacted with phosphorus phosphate in a dry inert solvent at 60–100 ° C, preferably with or trithian alcohols, this formula is reacted with dialkyl dithiophosphoric acid, where alkyl 5 is present in the Presence of aliphatic alcohol at its boiling point in vacuum and further processing, respectively and about 1447843 6 the obtained reaction product with an alkyl amine at 30-100 ° C. 2. The method according to p, 1, about t l and h and y - t; u and with the fact that the solvent used components of mineral oils or aromatic or alkyl aromatic hydrocarbons. Pro, gzu.-t C.Hj, TOjPSg C ,, 607 With „Нб4ЙО, 23 587 Indicator Anti-seize (EP) properties - tested by ZVP-method TGL 26890 A / 25/130/10 destructive load, kgf / cm VKA - load weld, kgf Table 607.9 42.1 37.0 1200 587e8 27,22,6 VET 23.37 25.19 1200 25 823,01,5 1200 table 2 Gear oil 50,100 CCT 3% trithioland dithiophosphate according to Example 4 1273 741 300/340 200/220 Indicator Anti-foam properties on TGL 29205 Antioxidant properties according to TGL 17,745 (72 hours at 5 liters of air per hour, slow leaf) 50% Centrifuged sediment,% Anti-corrosion properties according to TGL 21 140 Editor A. Ogar Compiled by L.Ivanova Tehred L.Oliynyk Order 6808/28 Circulation 464 VNShPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, 4/5 Raushsk nab. Production and printing company, Uzhgorod, st. Project, 4 Continuation of table 2 Gear oil 3% trithiol dithiophosphate in accordance with Example 4 a About ml, and 100 ml b 30 ml b 300 ml o ml with 120 ml 3.8 0.1 4.5 0.1 Korrozi korrozi is missing Proofreader L. Pilipenko Subscription