DE1255221B - Lubricating oil - Google Patents

Description

FEDERAL REPUBLIC OF DF UTSCHLAND

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

ClOm

i " P Al SjjS

C 1OM 169/00 B 48

German class: 23c-lfßi

Number: 1 255 221

File number: St 15883IV c / 23 c

Filing date: December 8, 1959

Open date: November 30, 1967

The invention relates to lubricating oils based on mineral or synthetic oils, the additives from new reaction products of phosphorus sulphide hydrocarbon products and for internal combustion engines, how diesel and car engines are suitable. The lubricating oils according to the invention have good cleaning and corrosion protection properties and prevent premature ignition, resinification and an increase in the need for octane.

Lubricating oils with additives from reaction products of phosphorus sulphide hydrocarbon products are already known. For example, US Pat. No. 2,316,082 describes lubricating oils with basic substances neutralized reaction products from a phosphorus sulfide and a hydrocarbon contain. U.S. Patent 2,688,612 discloses a process for making similar phosphorus sulfide-hydrocarbon reaction products known as lubricating oil additives. Then hydrolyzed ^ phosphorus sulfide hydrocarbon products with alkaline adsorbents before or after neutralization with basic substances, e.g. B. basic alkali or alkaline earth compounds, treated.

Surprisingly, it has now been found that the properties of lubricating oils by adding boron-containing, hydrolyzed phosphorus sulfide hydrocarbon products neutralized with amine bases are considerable can be improved.

The invention relates to a lubricating oil based on mineral or synthetic oils, thereby characterized in that it is 0.01 to 20 weight percent of one with an aliphatic amine or polyamine or hydroxyl-substituted aliphatic amine-neutralized reaction product from a hydrolyzed one Phosphorus sulfide hydrocarbon product with boric acid, boric anhydride, boric acid ester, boron phosphorus or contains borofluoric acids.

Any aliphatic compound having one or more basic compounds can be used as the aliphatic amine Be amino groups. Preferred amines are hydroxyl-substituted aliphatic amines, e.g. B. ethanolamine and triethanolamine, aliphatic polyamines and the aliphatic polyhydroxy polyamines. Very suitable aliphatic polyamines are alkylene polyamines having at least two primary amino groups, e.g. B. Ethylenediamine, propylenediamine, diethylenetriamine, diamylenetriamine, triethylenetetramine, tripropylenetetramine, Diethylene propylene tetramine, tetraethylene pentamine, tetrabutylene pentamine, diethylene dipropylene pentamine, Butylenediamine and dihexylenetriamine and mixtures thereof, also a crude diethylenetriamine, the smaller amounts of ethylene diamine and tri-lube

Applicant:

Standard Oil Company, Chicago, JIl. (V. St. A.)

Representative:

Dr. I. M. Maas, patent attorney,

Munich 23, Ungererstr. 25th

Named as inventor:

Donald Leroy Klass, Barrington, JIL;

Roger William Watson, Highland, Ind .;

Robert Edward Karll, Munster, Ind. (V. St. A.)

Claimed priority:

V. St. v. America 8 December 1958

(778576, 778 583, 778 606)

contains ethyl tetramine. Further examples are polyamines of the general formula RNH (CHa) ₈ NH ₂ , in which R preferably denotes an aliphatic chain with 10 to 18 carbon atoms, which are obtained by condensation of the corresponding amine with acrylonitrile and hydrogenation to give the corresponding diamine. Commercially available aliphatic polyamines of this type are hydrogenated condensation products of a dodecylamine (from coconut fatty acids) or an octadecylamine (from tallow fatty acids) and acrylonitrile.

Hydrolyzed phosphorus sulfide - hydrocarbon reaction products and their preparation are known (see US Pat. Nos. 2,316,082, 2,688,612 and 2,843,579).

The phosphorus sulfide - hydrocarbon reaction product contained in the mineral lubricating oils according to the invention preferably contains an olefin polymer as the hydrocarbon component, in particular a butene polymer.

Borophosphoric acid, a dry, non-hygroscopic powder, is also known and can be used according to the in U.S. Patent 2,375,638.

709 690/461

A particularly suitable process for the production of difluoroboric acid, a liquid, is in Journ. Amer. Chem. Soc, Vol. 57, 1935, p. 454, and consists in the reaction of B ₂ O ₃ with hydrogen fluoride.

The preparation of the reaction products described below is not patented here posed.

To 800 at a temperature of about 232 ⁰ C in a nitrogen atmosphere for .5 hours a hydrolyzed phosphorus sulfide-hydrocarbon reaction product is prepared by reacting 15.5 percent by weight of P ₂ S ₅ with a butylene with a molecular weight of about 750 with a phosphorus content of about received 4.3% and a sulfur content of about 7.5%, which is hydrolyzed with steam at about 148-205 ⁰ C. For easier handling, the hydrolyzate is diluted to an approximately 60% concentrate with a solvent-extracted Mid-Continent 5W mineral oil with a viscosity of approximately 38 SSU at 99 ^° C. and used as a starting material for the production of the additives.

example 1

The diluted hydrolyzate was extracted with isopropanol and water and reacted with 1 mole of ethylenediamine per mole of hydrolyzate. The basic amine salt formed was treated with a solution of 1 mole of boric acid in dioxane. The mixture was stirred at 60 to 80 ° C for 1 hour and then heated to 100 to 110 ⁰ C.

Excess dioxane was distilled off from the mixture, and traces of dioxane still remaining were removed by bubbling nitrogen through them. The product was oil soluble and clear and contained 1.79% Phosphorus.

The following summarized in tabular form Examples were essentially as described in Example 1, worked.

at
game Pretreatment
of the hydrolyzate Amine, crowd Acidity, amount solvent Reaction
temperature
⁰ C 2 Solvent extraction N-tallow propylenediamine, Boric acid, 1 mole Dioxane 60 to 80 about 1 mole 3 * Solvent extraction Ethanolamine, 1 mole Boric acid, 1 mole Dimethylformamide 140 4 * Solvent extraction Triethanolamine, 1 mole Boric acid, 3 moles Dimethylformamide 140 5 * Solvent extraction Ethylenediamine, 1 mole Boron phosphorus - 100 acid, 1.22 moles 6 * with sound Diethylenetriamine, 1.1 moles Difluoroboric acid, - 100 3MoI 7 * with sound Triethylenetetramine, Difluoroboric acid, - 100 1.1 moles 3.53 moles 8th* with sound N-tallow propylenediamine, Difluoroboric acid, - 100 1.1 moles 1.49 moles

* Filtered through clay before analysis.

To determine the cleaning effect of lubricating oils according to the invention and of lubricating oils with known additives from boron-free metal-containing neutralized phosphorus sulfide hydrocarbon products, as described in U.S. Patents 2,316,082 and 2,688,612, were motorized Lubricant tests carried out. For comparison, additive-free mineral oil and mineral oil were also used with the addition of sulphurized dipentene as a corrosion inhibitor checked.

The test was carried out in a Chevrolet Powerglide engine as follows:

The engine was operated for 1 hour at 500 rpm "no load and a further 6 hours at 2500 rpm and a power output of 33.5 kW. The oil temperature was during 1 hour 38 ⁰ C, while the 2nd and 3rd hour, 74 ° C and during the 4th to 7th hour 104 ⁰ C. the water temperature was such cycles during the 1st to 3rd hour 29 to 35 ⁰ C and during the 4th to 7th hour 76 to 82 ° C. A total of four The pistons were then examined for deposits and rated on a scale in which the rating number 10 corresponds to clean pistons and the rating number 1 corresponds to pistons with very heavy deposits.

rehearse Piston rating I. 5.9 to 6.3 II 5.3 III 7.2 IV 7.4 V 8.5 Vl 8.8 VII 8.7 VIII 9.1

Explanation:

I. Phenolextrahiertes Mid-Continent mineral oil having a viscosity of about 45 SSU at 99 ⁰ C. No additives.

II. 0.75 weight percent sulfurized dipentene in phenol-extracted mid-continent mineral oil with a viscosity of about 45 SSU at 99 ° C.

III. 3.9 weight percent barium-containing neutralized reaction product of P ₂ S ₆ and butylene polymer (molecular weight about 750 to 800) and 0.79 weight percent sulfurized dipentene in solvent-extracted mid-continent mineral oil, which contains a polyisobutylene polymer as a viscosity index improver, with a viscosity of about 62 SSU at 99 ^° C. Phosphorus content 0.055 percent by weight.

Claims (1)

5 6 IV. 6.6 percent by weight barium-containing neutral dipentene in phenol-extracted mid-conti- based reaction product from P ₂ S ₂ and butylened mineral oil with a viscosity of about polymeric (molecular weight about 750 to 45 SSU at 99 ° C. Phosphorus content 0.067 Ge 800) and 0.75 weight percent sulfurized weight percent. penten in solvent-extracted mid-continent 5 From the table above it can be seen that Mineral oil with a viscosity of about 45 SSU Lubricating oils with boron-containing additives according to the invention at 99 ° C. Phosphorus content 0.135 percent by weight (samples V to VIII) compared to known ones cent. Lubricating oils with boron-free additives (samples III and V. 3.74 percent by weight of the product according to Bei IV) and mineral oil without additives (sample I) and game 1 in phenol-extracted mid-continent mineral oil that contains only sulfurized dipentene Mineral oil with a viscosity of about 45 SSU (sample II), have superior cleaning properties. at 99 ° C. Phosphorus content 0.067 percent by weight _cent claim: VI. 4.27 percent by weight of the product after Bei- lubricating oil based on mineral or spiel2 in phenol-extracted Mid-Continent 15 synthetic oils, thus identifiable Mineral oil with a viscosity of about 45 SSU is characterized as being 0.01 to 20 percent by weight at 99 ° C. Phosphorus content 0.067 percent by weight with an aliphatic amine or polyamine cent. or hydroxyl substituted aliphatic amine VQ. 3.43 percent by weight of the product after in-neutralized reaction product from a game 3 and 0.75 percent by weight sulfurized 20 hydrolyzed phosphorus sulfide hydrocarbon Dipentene in phenol-extracted mid-conti product with boric acid, boric anhydride, boron nent mineral oil with a viscosity of about acid esters, borophosphoric or borofluoric acids 45 SSU at 99 ° C. Phosphorus content 0.067. weight percent. VHI. 3.73 percent by weight of the product according to the 25 Publications considered: game 4 and 0.75 weight percent sulfurized U.S. Patent Nos. 2,316,082, 2,688,612. 709 690/461 11.67 ® Bundesdruckerei Berlin