CS252527B1 - Heat and oxidation stable admixture into lubricating oils for gear mechanismes - Google Patents

Abstract

Lubricating oil additive composition for transmission mechanisms, which comprises: 1. Metallic, especially zinc, di-dithiophosphoric acid dialkyl ester of 1 to 20 carbon atoms in the -alkyl group 2. Hydroxyalkyl alkyl or alkenylphosphonic acid of formula s and RP — XR, XRf wherein R is alkyl or alkenyl mol. weight 300 to 2000, X is oxygen or sulfur and R * is hydrogen or O organic amine or imine, or a urea derivative, or -CnH2nOH, wherein n is 2 or 3, and at least 0 is per 1 phosphorus atom , 5 moles of -CnH2nOH groups. The additive further comprises at most 40 wt. pere. organic) sulphide-disulfide, disulphide and sulphurous sulfur compounds containing up to 50 wt. % bound sulfur.

Description

252527

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to thermally and oxidatively stable additions of organic sulfur compounds and phosphorus to the transfer mechanisms of the dithiophosphoric acid dialkyl esters and phosphonic acid derivatives.

Anti-wear additives for improving the high-pressure properties of lubricants, and especially lubricating oils for transmission mechanisms, are various chlorine, sulfur and phosphorus-containing organic compounds which, under extreme mechanical load conditions, are subject to frictional friction. In the case of elevated surface temperatures on the surface of the metal, the fine sorption and reaction films of the iron compounds are formed, and these are capable of protecting functionally machine components from pre-use.

The active ingredient is required not to have harmful side-effects due to good anti-wear properties. Some of the compounds used as anti-wear or high pressure additives are thermally small and decompose at elevated temperatures in the lubricated devices to form oil-insoluble substances. These are eliminated in the form of deposits and sludge, as a result of which the lubrication process may deteriorate. Other compounds react with the metal in such a way that, instead of producing a relatively stable surface film, there is corrosion of metal functional components or additional rusting due to air humidity. In silo-coated machine and gear mechanisms, especially for special vehicle gearboxes, oil temperatures reach 90 to 130 ° C on average and undesirable decomposition reactions and corrosion processes take place under such conditions, if the ma-zadlo used contains anti-wear additives. - sufficient thermal stability and unsuitable aggressive properties.

Some chlorinated hydrocarbon-labile and / or reactive-sulfur-containing additive additives exhibit such undesirable properties. Deficiencies are also found in some known organic compound additives containing phosphorus and sulfur, which exhibit counter-ionic properties. The salts of dithiophosphoric acid diesters, especially zinc, have been successfully used in motor oil shells for good antioxidant and anticorrosion properties, but also for the ability to prevent abrasion and wear on some of the engine components, such as hoist, cams, cylindrical inserts and piston rings. They are also recommended for use in mixtures with chlorinated hydrocarbons and their derivatives in gear oils (U.S. Pat. No. 4,120,224, French Pat. No. 1,487,224, British Pat. Nos. 847,193 and 960,623). However, the metal salts of dialkylphosphoric acid dialkyl esters are thermally stable and, with conventional heating tests at 120 ° C, larger amounts of deposits are deposited from the oil solutions after a 24-hour exposure to elevated temperature. For this reason, they are not suitable as anti-wear additives for oils for strong stressed transmission. Of the other phosphorus and sulfur compounds, the anti-wear effects of the phosphorus reaction products with terpenes (USP 3,060,166), unsaturated fatty acids or other fatty substances (French patent 1418 878, USP 3 200 072), and naphthenic acids (AO USSR 183 Or the products of olefin reactions with phosphorus sulfides, further treated with vinyl esters (USP3 089 852) or with fatty acid esters and lead oxide (USP 3196 110).

The metal or amine salts or imides and amides in the oil-soluble olefin reaction products of phosphorus sulfides or the corresponding alkenylthiophosphonic acids of the sasamotics do not exhibit anti-wear properties, but exhibit dispersing effects are thermally stable.

Podlá čs. of the invention AO 157 995 and 173 175 show good anti-wear, antioxidant and anticorrosive effects of an additive on the base of metal salts of dialkyl esters of dithiophosphoric acid and salts or amides and 1-amide thiophosphonic acid derivatives. Mixtures of dithiophosphoric and thiophosphonic acid derivatives may contain organic sulfur compounds, for example, dibenzyl disulfide or cross-linked hydrocarbons, thereby enhancing the anti-radiation characteristics of the additive. According to AO216297, the heat and oxidation-stable anti-deride and anti-gypsum additive in the transfer oils contain, in a mixture of dithiophosphoric and thiophosphonic acid derivatives AO 157 995 and AO 173 175, a sulfur-containing hydrocarbon containing 15 to 40 wt. % of bound sulfur, wherein per wt. part of the cross-linked hydrocarbon is 1 to 4 wt. parts of the dithiophosphoric and thiophosphonic acid derivatives whose ratio is 3: 7 to 7: 3.

We have found that AO 157 995, AO 173 175 and AO 216 297 specific additive compositions are improved when hydroxyalkyl esters prepared by the reaction of derivatives are used as phosphonic acid derivatives in mixtures of dialkyl dithiophosphoric acid dialkyl esters. phosphonic atiophosphonic acids with alkylene oxides.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat and oxidatively stable additive of organic sulfur compounds and phosphorus to lubricating oils for transmission mechanisms comprising 25 to 75 wt. % dithiophosphoric acid dialkyl ester metal having 1 to 20 carbon atoms in the alkyl group and 25 to 75 wt. % of an alkyl or alkenyl phosphonic acid derivative having a hydrocarbon chain molar molarity; a weight of 300-2000, wherein the alkyl or alkenylphosphonic acid derivative is a hydroxyalkyl ester of the general formula 2S2527

ν 'o η il & bo Μ

f /

XR wherein R is alkyl or alkenyl mol. X is oxygen or sulfur and R 'is hydrogen or an organic amine or imine such as diethylenetriamine or ethanolate or a urea derivative, or -CnH2nOH wherein n is 2 or 3 wherein 1 is a phosphorus atom there is at least 0.5 molar of the -CnH2nOH group and the metal in the dithiophosphoric acid dialkyl ester salt is the preferred one. The additive may further comprise at most 40 wt. % sulfuric acid sulphide, disulphide and sulfur sulphide-containing sulfur compounds up to 50 wt. %. The dialkyl ester dithiophosphoric acid salts present therein are obtained by reacting aliphatic alcohols having 1 to 20 carbon atoms or mixtures of several phosphorous sulphate alcohols to form dithiophosphoric acid alkyl esters of the general formula (ROjzP — SH which react with the oxides, hydroxides The hydrophilic oil is a soluble zinc salt of dithiophosphoric acid dialkyl esters containing 6 or more carbon atoms with a alkyl substituent or 1 to 5 carbon atoms in the mixed dialkyl esters of di-phosphoric acid.

The phosphonic acid derivatives of the invention are the products of the reaction of olefins with a molecular weight of 300-2000 based on polymer propene and / or butenes with phosphorous sulphide or a mixture thereof with phosphorus pentoxide. The alkenylphosphonic and alkenylthiophosphonic acids and their thioanhydrides formed in the reaction are further treated by reaction with ethylene oxide or propylene oxide to give hydroxyalkyl esters of phosphoric and thiophosphonic acids. The enhancement of the conversion to phosphonic and thiophosphonic acids is subject to the preferred hydrolysis products of the phosphoric acid reaction with the polymeric olefin prior to treatment. In the composition based on the metal salt of dithiophosphoric acid di-alkyl ester and the phosphonic acid derivative, part of the two components in the amount of at most 40 wt. % to replace the organic sulfur compound with sulfides, disulfides, or cross-linked alkenes. Such compounds are, for example, dibenzyl disulfide or sulphated alkanes and terpenes with a content of up to 50 wt. % of the bound sulfur, for example the sulfur-containing tetramer-propylene or the sulfur-containing fraction of 10 to 20 carbon atoms, preferably more than 20 wt. % bound sulfur. The additive of the invention may be supplemented by other components which are commonly used to provide functional and physical characteristics of lubricating agents for automotive and industrial transmission mechanisms, for example corrosion inhibitors and corrosion inhibitors, anti-fouling agents, de-emulsifiers, depressant and viscosity modifier. Thus, the complex effect of the additive without interfering with the other component present in the lubricating oil is ensured. The additives according to the invention are characterized by a very good anti-wear effect of the in-use laboratory evaluations and, at the test values of the FZG test line, according to Niemanna, satisfy at 12. load steps with a yield of 3 to 6 wt. additives in oil.

In terms of heat-oxidation stability, gear oils with underlay additives in the test according to ČSN 65 6235 comply with the catalytic feeding of the medium (at 150 ° C for 100 hours it is 163 ° C in the FIAT test).

Test oils with additives according to the invention meet the requirements of the corrosion testing for copper according to ČSN 65 6075 and for steel according to ČSN 65 6249 and also the test according to Bo-kowiecki (Schweizer Archiv 19, 22-31, [1953]). Examples: Base Oil: Selective raffinate containing 1 wt. % of the viscosity modifier of polymethacrylate resin, 0.005 wt. % rusting inhibitor, 0.002 wt. % polysiloxane and 0.3 wt. % deemulsifier. Viscosity 15.4 mm 2 s -1 at 100 ° C, viscosity index 90.7, dynamic viscosity 43.2 Pas at -18 ° C.

Ingredients used:

Component A. Dithiophosphoric acid diester metal salt Al-C 4 -C 6 alkyl; metal: Formula A-C 1-6 alkyl; metal: Zn

Component B. Alkenylthiophosphoric acid hydroxyalkyl ester based on 252527 Sample B1 - Polybutene Diam. molecular weight 940 and ethylene oxide, phosphorus: ethylene oxide 1: 1 (mol) sample B.2 - polypropylene diam. molar mass 720 and propylene oxide, phosphorus: pro-pylene oxide 1: 0.8 (mol)

sample B.3 - as sample B1, phosphorus: ethylene oxide 1: 0.5 (mole), treated with urea, contained 2.2 wt. % P, 1.6 wt. % S, 0.7 wt. % N sample B.4 - polybutene diam. mol. 940, Ba salt of alkenylthiophosphonic acid

Component C. Organic Sulfur Compound

sample Cl - crosslinked tetramer propylene 26 wt. % S sample C.2 - dibenzyidisultld

In evaluating the application properties, the following methods and evaluations were used: 1. Anti-wear and anti-gypsum properties: a) on a four-tube instrument: I. CKS assessment according to ČSN 65 6254 (back-up load) II. VUO assessment according to ČSN 65 6254 b) on Timken instrument: the oil film strength is assessed in the area of friction using co-constant material by test element c) on the FZG test gearbox by Niemann with test-wheel width of 20 millimeters (method A20 / 8.3 / 90 ). It determines the correct degree of load at a gradual increase in load from 1 to 12 degrees (test run of 15 min, initial oil temperature of 90 and C) at which the abrasion of the test gear, determined by weighing, exceeds the limit peace. 2. Thermal-Oxidation Stability: was tested in a FIAT gearbox under specified thermal and mechanical oil loading at a continuous and constant air supply at 163 ° C for 50 hours. The test evaluates the increase in oil viscosity, insoluble matter content in HEO, and weight loss of inserted Cu-plate. 3. Corrosion: a) for honey according to ČSN 65 6075 at 120 ° C for 4 hours. The test plate is visually evaluated by four steps b) on the steel plate. the test gives Bukowieckeh at 120 ° C for 7 days followed by saturated aqueous vapor at room temperature for 168 hours. Evaluates the change in weight of the test plate and the degree of rusting: 0 - surface without change; 1 - change in gloss; 2 - sparse rust over surface time; 3 - continuous rust layer. The evaluation results are presented in the table.

Claims (2)

252527 10 Sample cleanStrength of additive: A.l wt. % A.2 wt. % B.l wt. % B.2 wt. % B.3 wt. % B.4 wt. % C.I wt. % C.2 wt. % Contents of the composition in oil. % Evaluation results: 1.1 Anti-tumor and anti-doper effects: 1.1 Stvordul device a) CKS value kg / kg b) VUO value 1.2 Timken OK Lb 1.3 Gearbox FZG A20-8.3 / 90 - unsatisfactory stage 2. Thermal oxidation stability 2.1 Gearbox FIAT (163 And (h) the viscosity increases by 1% and b) insoluble in HEOhm. ° / oc) weight lossCu-platelets g 3. Corrosion rate 3.1 for copper according to CSN 65 6075 3.2 for steel according to Bukowiecke a) after 168 h in oil at 120 ° C, change of mass g / m 2 b) after a] in vapor-saturated vapor , change in g / m2 cj degree of rusting Table 1 2 3 4 75. 50 50 50 25 50 50 50 4.5 4.5 4.5 4.5 200 / / 224 42.5 200 / / 224 46.3 200 / / 224 47.1 200 / / 224 51.7 54 56 56 12 12 12 12 0.07 0.10 0.15 0.12 1.04 1.20 1.10 1.15 0.61 0.60 0.55 0.51 1 1 1 1 —0.14 -0.02 - 0.04 - 0.02 -0.08 1 +0.17 1 +0.09 1 +0.05 1 OBJECT OF THE INVENTION 35 50 50 70 35 45 30 30 5 50 4.5 4.5 4.5 4.5 200/398/300/178 / / 224/447/320/200 45 67.4 58.9 45 55 55 55 47 12 12 12 12 0.08 1.50 1.40 13 2 1.11 1.13 0.24 0.74 0.63 0.76 0.72 0.22 1 1 1 1 -0.12 -0.13 -0.06 —0.10 — 0.07 - 0.04 +0.07 +0.08 1 1 1 1 CLAIMS 1. A heat and oxidatively stable addition of organic sulfur and phosphorus compounds to lubricating oils prior to the transmission mechanisms, comprising 25 to 75 wt. About a metal salt of dithiophosphoric acid di-alkyl ester having 1 to 20 carbon atoms in the alkyl group, 25 to 75 wt. % of an alkyl or alkenylphosphonic acid derivative having a hydrocarbon chain of mole. characterized in that the alkyl or alkenylphosphonic acid derivative is a hydroxyalkyl ester of the general formula RP - XR and ore P — X-PR / i! In which R is alkyl or alkenyl mol. X is oxygen or sulfur and R 'is hydrogen or an organic amine or imine, e.g., diethylenetriamine or ethanothiamines, or a urea derivative, or --CnH2nOH wherein n is 2 or 3, wherein 1 is 1 atom phosphorus accounts for at least 0.5 mole of -CnH2nOH and the metal in the dithiophosphoric acid dialkyl ester salt is preferred. 2. A heat and oxidation-stable lubricant oil additive for the transmission mechanism of claim 1, further comprising at most 40 wt. % of an organic sulfur compound such as sulfides, disulfides and sulfuric alkenes containing up to 50 wt. Of sulfur.