CS272616B1 - Agent for improvement of admixtures' and lubricating oils' demulsifying properties - Google Patents

Abstract

A preparation for improving the demulsifying nature of additives and lubrication oils, particularly containing organic compounds of sulphur and phosphor of the type of salts of derivatives of dithiophosphate and thiophosphonate acids and organic sulphides and polysulphides, which are composed of derivatives of imidazoline, containing an alkyl or alkenyl substituent with 10 to 25 carbon atoms and preferably 1 to 2 molecules of carboxyl acid, bound in the form of salt or amide. Up to 25 % of the imidazoline derivative can be replaced by a salt of a metal of alkaline earth or amino salt of petroleum sulphonic or alkyl benzene sulphonate acid of molar mass 300 to 1000.

Description

The invention relates to a composition for improving the demulsifying properties of additives and lubricants. oils, in particular for gear and other retracted mechanisms.

It is known that petroleum oil raffinates containing organic sulfur and phosphorus compounds as anti-abrasive additives are prone to form hardly separating emulsions in the presence of water, which can cause rusting of steel components of stressed machinery. The susceptibility to the formation of aqueous emulsions is particularly apparent in lubricating oils, in which the compositions of metal salts of dialkyl dithiophosphoric acid salts and thiophosphonic acid derivatives, optionally containing organic sulfur compounds of the type sulphides of the Czech Republic, are used as anti-wear and high pressure additives. No. 157,995 or AO 173,175, AO 216,297, AO 252,527 and AO 254,195.

Ampholytic compounds of the type of reaction products of polyoxyalkylene amines with dicarboxylic acids (U.S. Pat. No. 4,151,173) or reaction products of polyisocyanates with polyamine and a sulfuric acid derivative (U.S. Pat. No. 4,016,101) are known as lubricating oil demulsifiers.

Imidazoline derivatives are known as rust inhibitors for lubricating oils, e.g. salts of carboxylic acids and 1-alkyl-2-aminoethylimidazoline according to U.S. Pat. patents 139 297 and 148 307.

However, their effect of improving the demulsifying properties of additives and lubricating oils, in particular containing organic sulfur and phosphorus compounds, is not known.

We have now found that imidazoline derivatives suppress the susceptibility to the formation of emulsions with water, in particular with additives containing in particular organic sulfur and phosphorus compounds used in stressed machinery and transmission equipment.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for improving the demulsifying properties of additives and lubricating oils, in particular containing organic sulfur and phosphorus compounds of the dithiophosphoric and thiophosphonic acid salts and organic sulfides and polysulfides.

CH, CH,

I

Ν Ν - ΟΗ, ΟΗ, ΝΗ, \ /

I

B wherein R is alkyl or alkenyl of 10 to 25 carbon atoms, e.g. heptadecyl, which preferably contains 1 to 2 carboxylic acid molecules bound in the form of a salt or amide.

In admixture with the organic sulfur and phosphorus compounds, 1 to 10% by weight of the imidazoline derivative per active ingredient is used, wherein a portion of up to 25% by weight of the imidazoline derivative can be stolen with an alkaline earth metal salt or an amino salt of petroleum or alkylarylsulfonic acid. weight 300 to 1000.

The improved demulsifying properties are particularly useful for additives and lubricating oils whose anti-abrasion and high-pressure properties are ensured by a mixture of a metallic, in particular zinc, dialkyl dithiophosphoric acid salt with a metal or amine salt or an alkenyl thiophosphonic acid ester with an average hydrocarbon chain weight of 500 to 500 mol. pod čs. No. 157,995 or AO 173,175. Suitable alkenylthiophosphonic acid derivatives are prepared by reacting butene or propene oligomers with phosphorus pentasulfide and after hydrolysis the reaction product is treated with an alkaline earth metal hydroxide, an organic amine or urea to the corresponding salt or amide or alkoxylation to an ester.

Improvements in the de-emulsifying properties of the present invention are also evident in additives and lubricating oils which contain, in addition to salts and derivatives of dithiophosphoric and thiophosphonic acids, organic sulfur compounds of the sulfide and polysulfide type, e.g. products of reaction of olefins with sulfur according to AO 216 297, AO 252 527 and AO 254 195.

CS 272 616 B1

The composition according to the invention can be used in the preparation of additives with anti-abrasion and antioxidant properties based on organic sulfur and phosphorus compounds, thereby obtaining complex effects when used in lubricating oils, in particular for gear and other retracted mechanisms, and providing deemulsifying and inhibitory effects. against corrosion and rust of steel. The composition according to the invention can also be used directly in the preparation of a lubricating oil, if necessary, when the imidazoline derivative and optionally the petroleum or alkylarylsulfonic acid salt is added to the oil raffinate, for example as an additional component in addition to the organic sulfur and phosphorus compounds.

The imidazoline derivatives according to the invention are usually products of the reaction of diethylenetriamine and carboxylic acids having 10 to 26 carbon atoms, whereby excess carboxylic acid forms salts or amides of carboxylic acid and 1-alkyl-2-aminoethylimidazoline e.g. pod čs. No. 139,297, which are very effective as demulsifiers, as well as corrosion and rust inhibitors of structural steels in lubricating oils, especially in admixture with minor amounts of alkaline earth metal salts or of the amine salt of petroleum alkylarylsulfonic acid. Calcium, but also magnesium and barium salts are usually used in the form of a concentrate in petroleum oil containing 25 to 45% by weight. % of the active substance, which may be neutral or low-base with a basic value of up to 40 mg KOH / g or even medium to high-base with a total basicity of up to 400 mg KOH / g. At higher basicity, the oil concentrates of sulfonic acid salts contain carbonates or alkaline earth metal hydroxides in a melt of colloidal dispersions. Alkanolamine or alkylamine salts, e.g. dibutylamine salt of petroleum or alkylbenzenesulfonic acid. Salts e.g. didodecylbenzenesulfonic acid or even sulfonic acids with C10-C30 paraffin-based alkyls. The means for improving the demulsifying properties of additives and lubricating oils according to the invention does not have a negative effect on the anti-abrasion, high pressure and antioxidant action of the organic sulfur and phosphorus compounds contained therein, or on other additives which satisfy the requirements of viscous, theological or foaming properties or pour point.

Lubricating oils for the retracted transmission mechanisms of the present invention meet the corrosion protection requirements of DIN 65 62 49 and the demulsifying properties of Article 10 of PUD 9-403-87, which is evident from the evaluation of additives and lubricating oils according to the invention compared to base oils without additives and containing sulfur and phosphorus compounds.

Examples:

A - Used base oils

A1 - A mixture of selectively refined vacuum distillate and medium-pressure paraffinic hydrotreated raffinate, dewaxed in a solvent process containing 0.5-1 wt. % polyalkyl methacrylate additive and 0.001% polysiloxane, viscosity 7.9 mm s at 100 ° C, viscosity index 92, flash point 218 ° C.

A2 - Oil raffinate, obtained by recovering spent oils by treatment with sulfuric acid, neutralization, melting and bleaching earth, containing 0,9% by weight % polyalkyl methacrylate additive and 0.001% polysiloxane; viscosity 14.8 mm 2 s -1 at 100 ° C, viscosity index 90, flash point 231 ° C.

B - Additives of organic sulfur and phosphorus compounds

B1 - A mixture of 50% zinc salt of dialkyl dithiophosphoric acid alkyls and Cg ¢ 7% Zn; 7.7% P; 15.2% S) and 50% of the product of the reaction of alkenyl thiophosphonic acids with urea (oil concentrate: 1.9% P; 1.5% S; 0.35% ΪΓ - MÁPKI 401).

B2 - A mixture of 60% zinc dithiophosphoric acid dialkyl ester with n-alkyl Cq-C18 (7.8% Zn; 7.3% P; 14.5% S) and 40% calcium molar alkenylthiophosphonic acid calcium salt. 760 (oil concentrate: 2.3% P;

1.6% S; 2.5% Ca).

B3 - A mixture of 33.3% zinc dithiophosphoric acid zinc salt as in B1; 33,3 $

CS 272 616 B1 Alkenylthiophosphonic acid diethanolamine salt with an average molecular weight of 920 (2,2% P; 2,0% S; 0,6% R) and 33,4% of sulphurated hydrocarbons (alkyl sulphides) containing 26,5% hm. S (MP-27)

C - Additives for improving the demulsifying properties

1-Heptadecenyl-2-aminoethyl imidazine CI (1 mol) and elainic acid (2 few) - (Idazox 2-0).

C2-10-alkyl (C1-4 and C1-4) -2-aminoethylimidazoline.

- Calcium salts of petroleum sulphonic acids - Oil concentrate 30% (Petrosulphonate 30).

C4 Dibutylamine salt of alkylbenzenesulfonic acid (alkyl C1-4-Ogg) - oil concentrate 40%.

table

Sample number 1 2 3 4 5 6 7 IN Component A: type -% A 2-J00 A2-95.5 A2-95,30 A2-95,3 A1-94,0 AI-93.80 A2-95.3 Component B: type -% - Bl- 4,5 Bl- 4,50 Bl- 4,5 B3- 6,0 B3- 6,0 B2- 4,5 Component C: Type -% - 01- 0.186 03- 0.024 Cl- 0.2 01- 0.18 C4- 0.02 C2- 0.18 C3- 0.02 evaluation results: 1. De-emulsifying properties: Separated water: ml / 10 min. 10 0 34 28 0 32 30 2. Protective action against v / rust: Pe: degree 2 3 0 1 3 0 1 3- Anti-Abrasion Properties: PZG ^ Transmission Test ^ Method A20 / £ ^ 3/90 - Grade Method AI 0 / 8.3 / 90 - Grade - above. 12 nad 12 nad 12 12 12 above. 12 _ 1

notes:

1 / Water separation of at least 20 ml / 60 min is required.

2 / Compliant grade. 0 - without rust and 1 - degree of corrosion; unsatisfactory: miema / 2 degree and strong corrosion 3 · degree /

3 / Grade 12: compliant

Claims (3)

OBJECT OF THE INVENTION Composition for improving the demulsifying properties of additives and lubricating oils, in particular containing organic sulfur and phosphorus compounds of the type of salts of dithiophosphoric and thiophosphonic acid derivatives and organic sulfides and polysulphides, characterized in that it contains, as active substance, an imidazoline derivative of the formula I CS 272 616 B1 CH, -CH, I I NN - CH ₂ CH ₂ NH ₂ . (I), χ / I E in which H is alkyl or alkenyl of 10 to 25 carbon atoms, e.g. heptadecyl. 2. A composition according to claim 1, characterized in that it contains a carboxylic acid having from 2 to 25 carbon atoms in a ratio of 1 mol of the imidazoline derivative of the formula I and 1 to 2 mol of the carboxylic acid. 3. A composition for improving the demulsifying properties of additives and lubricating oils according to claim 1, characterized in that it comprises 0.5 to 25 wt. % of an alkali earth metal salt of petroleum or alkylarylsulfonic acid mol. weight 300 to 1000.