DD140149A1 - METHOD FOR PRODUCING HIGH PRESSURE ACCESSORIES - Google Patents

Abstract

The invention relates to a process for the preparation of High pressure additives, especially for high performance EP oils, the in addition to an excellent pressure capacity a good Possess antioxidant and Äntiverschleißwirkung. It was found, that the ammonium salts of. Dialkyldithiophosphoric acids whose. Alkyl radicals contain trithiolane-type structural elements, such Represent high pressure additives. These are obtained when Tr.ithianalkohoie with phosphorus pentasulfide in dry, inert Solvents reacted at temperatures of 60 to 100 ° C, or Dialkyldithiophosphorsäuren whose alkyl radicals in the range C4 to C-J5 are, with'Trithianalkoholen at the boiling point The respective alkyl alcohol are transesterified in vacuo and the respective reaction product at temperatures up to 100 ° C with organic amines is converted into the ammonium salt.

Description

Field of application of the invention

The invention relates to a method for producing high-pressure additives _? especially for high-performance EP oils.

Characteristic of the known technical solutions

It is known to use dithiophosphates as antioxidants or anti-wear additives. Such additions are prepared by reacting 1 mole of phosphorus pentasulfide with 4 moles of alcohols at temperatures of 100 to 120 ⁰ C initially 2u Dialkyldithiophosphorsäuren. These phosphoric acids are oily, viscous, non-crystallizing substances that can not be distilled without decomposition. The dialkyldithiophosphoric acids are converted to oil-soluble compounds by IT neutralization with hydroxides or alkoxides of Ba, Mg, Oa, Al, Zn or Sn, with organic bases or polyethyleneamine. "Dialkyldithiophosphates thus obtained are very good at inhibiting oxidation and have, to a limited extent, high-pressure properties.

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Object of the invention.

The aim of the invention is to provide a process for the production of high-pressure additives, in particular those for gear lubricants that designed to produce high-pressure additives with improved EP properties cost.

Object of the invention 10

The object of the invention is to provide a process for producing high-pressure additives which makes it possible to produce high-pressure additives, in particular for gear lubricants, which, in addition to excellent pressure absorption capability, provide the lubricant with a good antioxidant and anti-oxidant effect.

give a wear effect and open it with the gearbox. are compatible.

Features of the invention 20

It has been found that compounds comprising ammonium salts of dialkyldithiophosphoric acids whose alkyl radicals contain trithiolane-type structural elements fulfill all the requirements for a punching pressure additive according to the task. These compounds are prepared by reacting either trithiane alcohols with phosphorus pentasulfide in dry inert solvents at temperatures of 60 to 100 ⁰ C, preferably 80 ⁰ O, or dialkyldithiophosphoric acids whose alkyl radicals in the range C ₂ , to C *, -, with trithiane alcohols The boiling point of the respective alkyl alcohol is reacted in vacuo and the reaction product is in each case reacted at temperatures of 0 to 100 ⁰ C with organic amines to the ammonium salt of dithiophosphoric acid. As Trithianälkohole compounds of general I ¹ Or-35 come

7 7

in which R _{1 is} -OH, -CH ₂ OH, - (CH 3 OH-, CH ₂ OH, R ₂ H or one of the groups of R ₁ is preferably used. The solvents used are mineral oil components, aromatics or alkylaromatics Use, as organic amines primary and / or secondary allylamines of chain length C ^ to Cp4 or aryl or arylalkylamines and corresponding amines with cycloaliphatic components in the range of 6 to 24

15 C atoms.

embodiments

Example 1 · ι.

In a sulphonation flask equipped with a mechanical stirrer, reflux condenser and gas inlet tube, 35% of 8-endo-hydroxy-inethy1, 3, 4, 5, 5-exo-trithiatricyclo J5.2.1.0 high 2,6J-decane (a) dissolved in 150 ml of dry benzene and heated with stirring and passing nitrogen in the reflux to 80 ⁰ C and treated with 9.3 g of phosphorus pentasulfide portionwise. Subject 4 hours, the P ₀ S ₅ almost completely dissolved "The residue is filtered off and the benzene in the Yakuum removed to the extent that a solution is formed, the di resulting in 50 ml 0.027 mol aer (3,4,5 ~ exo-trithiatricyclo J5 , 2 _# 1 «O high 2 _s 6] -decan-8-endo * methoxy) -dithiophosphoric acid (B) contains» 50 ml of this solution are mixed with 2,2 g of butylamine and heated under reflux until Z'Um boil « , Compartment 30 minutigem boiling the solvent is completely separated in Yakuuia · you get the

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n-butylammonium [di (3, ⁱ i ₉ 5-estr: o-trithiatricyclo [5 · 2.1.Ο high 2,6] decane-8 ~ endo-meth.oxy) j dithiophosphate.

Example 2

50 ml of the obtained according to Example 1 benzene dithiophosphoric acid are cooked with 5 »9 S dodecylamine for 3 minutes in the 'reflux. Thereafter, the solvent is distilled off in vacuo. The dodecylammonium {di (3,4,5-exo-thithiatricyclo [5.2.1.0 high 2,6J-decane-8-endo-mathoxy)} dithiophosphate is obtained.

Example 3

27 g diamyl dithiophosphoric acid are mixed in a distillation flask with 22 g of compound A and slowly added in an oil bath under vacuum. (0.3 Torr) initially heated to 70 ⁰ O, later heated to 90 ⁰ C bath temperature, wherein the cleaved amyl alcohol distilled off slowly within 4 hours.

20 g of the resulting AeqtI- (3,4,5-exo-trithia.tricyclo [5.2.1.0 high 2,6] -decane-8-endo-methoxy) -dithiophosphoric acid - (G) are dissolved in 100 ml of dry Benaol and heated to boiling with 9.5 g of dodecylamine for 30 minutes under reflux. Subsequently, the solvent is removed in vacuo. Ss, the dodecylammonium salt of C remains.

Example 4

111.6 g of dodecyl alcohol were treated with 33.3 g of P ₂ Sj- in 100 ml of dry benzene as Example 1 to didodecyldithiophosphoric acid (D) and separated.

74.6 g of compound D are mixed with 35 »3 S of compound A and slowly heated in a distilling flask at a pressure of 0.2 Torr to 120 ⁰ C bath temperature and distilled off within 5 hours 24.2 g of dodecyl alcohol. The remaining dodecyl (3,4,5-exo-trithiatricyclo [5.2.1.0 high 2,6j-decane-8-endo-methoxy) -dithiophosphoric acid (Ξ)

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is emulsified in gasoline · The compound E deposits as a viscous mass on the ground.

25 g of compound E are in 200 ml of dry benzene ge. dissolved and refluxed with 9.3 g of dodecylamine for 30 minutes. As described in Example 1,

The solvent is removed and the dodecylammonium is obtained. salt of compound E.

Example 5 10

As in Example 1 52 g of 2 Athylhexanol with 22.2 gp £ ^S 5 in 80 ml of absolute benzene to di- (2-ethylhe: kyl) -dithiophosphorsäure (F). 44 g of this compound are mixed with 27.3 g of compound A and slowly heated to 120 ⁰ G in a distillation flask in an oil bath at a pressure of 2 Torr.

In the course of 5 hours distilled off the split 2 ~ lthyl hexanol. The residue obtained quantitatively is 2-ethylheyl- (3 ₎ 4,5-exo-thithiatricyclo [5.2.1.0-highly 2,6] -decane-8-endomethoxy) -dithiophosphoric acid (G).

10 g of this dithiophosphoric acid are dissolved in 100 ml of dry benzene and boiled with 4.2 g of dodecylamine for 30 minutes at reflux. Subject to distilling off the solvent remains the dodecylammonium salt of the compound G.

Example 6.

As in Example 4, 126 g of Bidodecyldithiophosphorsäure- with 60 g of the compound A uneesterified. The compound A word6 not purified by vacuum distillation, but heated in vacuo from 0j1 Tcrr to 100 ⁰ G and thereby freed from unreacted starting components

 The eliminated dodecyl alcohol is distilled off. 50 S öss obtained reaction product are suspended in 200 g of G 200 basic gear oil and combined with a heated solution of 18.5 g of dodecylamine in 400 g of transmission base oil "Ss creates a clear, stable oil solution of the Dodecylammoniumsaizes the compound Ξ.

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Example 7

63 g 4 g of compound D are suspended in 100 g of gearbox oil G 1oo and treated with 30 g of compound A and slowly heated in an oil bath in vacuo, the bath temperature reaching a final value of 14o ⁰ C. Within 4 hours at 1oo ⁰ C and o, 8 Torr 2o, distilled off 3 dodecyl alcohol. This gives the compound E in the transmission base oil. To this mixture is added under Eühren 8o at ⁰ C 24.6 g of dodecylamine, to give a clear solution of the Dodecylammoniumsalzes the compound E is formed.

Compared to the known dialkyl dithiophosphates, the trithiolane-dithiophosphoric acid compounds according to the invention have much better EP properties, more favorable antisehumid properties and a very good compatibility with the customary transmission materials. They also have the necessary for the formulation of gear oils good Gebrauchsigensahaften the Zinkdialkyldithiophosphate, such as anti-oxidation and anti-corrosion and are therefore suitable high pressure additives for the formulation of gear oils of the highest performance class TM 5 to TGL 2116o, as can be seen from Table 2. "The known dialkyldithiophosphates allow maximum formulation of gear oils of performance class TM 3 ·

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List of abbreviations for the chemical compounds A S

[5.2.I.O high 2.6] decane

B Di (3,4,5-O2O-trithiatricyclo [5.2.1.0 high 2,6] decane ~ 8-endo-methoxy) -dithiophosphoric acid

G Amyl- (3,4,5-e2: o-trithiatricyclo [5.2.1.0 high 2,6J-decane-8-endo-methoxy) -dithiophosphoric acid

D didodecyldithiophosphoric acid

33 Bodocyl- (3, 5, 5-S2CO) trithiatricyclo [5.2.1.0 high-2, delta-decane-8-endo-methosyl) -dithiophosphoric acid

5 ¹ di (2-ethylhexyl) dithiophosphoric acid

G 2-ethylhexyl- (3,4,5-exo-trithiatricyclo [5.2.I.O high 2,6J-decene-8 ~ endo-2ietho2qy) -dithiophosphoric acid

Table 1

product

Sum of terms 1

MolmassQ analysis (1 calculates Almen-Wieland limit load

2 found) (200 min-J, after each % S 100 min "* i + 50 kp)

Addition to the mineral

607.9 1 2 oil in% 1200 ή-butylammonium salt of B. O ₂₀ Ho ₄ NO ₂ PS ₈ (Example 1) 719 42.1 37.0 2 % 1200 Dodecylammonium salt of B. C ₂₈ H ₅₀ NO ₂ PS ₈ (Example 2) 587.9 35.6 30.5 2 % 1100 Dodecylammonium salt of OO ₂₅ H ₅₀ NO ₂ PS ₅ (Example 3) 27.2. 24.6 1 % 1200 Do de cy! Ammonium alz of EO ₃₂ II ₆₄ NO ₂ S ₅ P (Example 4) 23.37 21.19 1 % 1200 Dodecylammonium salt of GO ₂₈ H ₅₆ NO ₂ PS ₅ (Example 5) 25.8 23.0 1.5 %

2 parts 2

transmission oil

= 1oo cSt with

5ο-

3 ft of trithiolane 3 $ of zinc dithiophosphate (2 ethyl according to Example 4 hexyl) dithio ". Phosphate

EP behavior

- Test according to the ZVP method TGL 2689o A / 25 / 13o / 1ο Damage

- VKA welding value

> 1273

3oo / 34o

741

2oo / 22o

Antischaumverhaiten a ml a 100 ml according to TGL 292o5 b 3o ml b 3oo al c ml c 12o ml Antiosidationsverhalten according to TGL 17 745 (72 h at 12o ⁰ C, 5 1 air / h, Cu sheet) 3.8 4.5 Centrifugal sludge [γ>] 0.1 0.1 Anti corrosion behavior none none after TGL 21 14o corrosion corrosion

Claims (4)

Claim for invention 1 · Process for the preparation of high-pressure additives based on dithiophosphates, characterized in that either trithiane alcohols with phosphorus pentasulfide in dry _s inert solvents at temperatures of 60 to 100 C, preferably 80 ⁰ O reacted or Dialkyldithiophosphorsäuren whose alkyl radicals in the range C ^ Ms C ^ transesterified with Trithianalkoholen at the boiling temperature of the alkyl alcohol in vacuo and the reaction product is reacted at temperatures of 0 ⁰ C to 100 ⁰ G with organic amines · 15 20 25 2. The method according to item 1, characterized in that as trithiane alcohols compounds of the general formula H ' ^H 1 in the E ^ -OH, -CH ₂ OH, - (CH ₂ ) _n 0H, -CHHOH [groups of E ^. means to be used E ₂ H or one of the 3. The method according to item 1 and 2, characterized in that are used as solvent mineral oil components, aromatics, alkylaromatics. 4. The method of item 1 to 3 "characterized in that as organic primary amines and / or secondary alkylamines having a chain length up to C ^ O _{2 / i} or aryl or arylalkyl amines or corresponding amines with cycloaliphatic components in the range of 6 to 24 carbon Atoms are used.