DE1154219B - Lubricating oil - Google Patents

Description

DFUTSCHES

PATENT OFFICE

S 73168 IVc / 23 c

REGISTRATION DATE: MARCH 27, 1961

NOTICE
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: SEPTEMBER 12, 1963

It is known that marine diesel engines are often operated with heavy fuels, for example arise as residues in the vacuum distillation of petroleum and a proportionate have high sulfur content. When such fuels are burned, acidic combustion products are formed in the form of SO2 or SO3, which lead to undesirable corrosion phenomena in the engine, especially in the cylinders and bearings. Experience has shown that this Corrosion cannot be remedied by the usual antioxidants. Preferably In practice, lubricating oils that contain compounds as additives have proven themselves which neutralize the sulfur, especially strongly basic naphthenates of metals Group II of the periodic table. Unfortunately, these additives in turn cause one heavy wear on the bearing metals, especially if they contain lead and copper. Such naphthenate-containing Lubricating oils therefore have when used as z. B. crankcase lubricants have considerable disadvantages, although they in themselves the neutralize acidic combustion gases and thus the direct damaging effects of sulfur Reduce.

It has been found that this is specifically due to the presence of basic naphthenates in the lubricating oils Wear damage caused can be largely reduced if the lubricating oil mixture based on a hydrocarbon lubricating oil in addition to a smaller proportion of one Naphthenates of a metal of group II with a basicity above 400 also have a smaller proportion of an alkyl derivative of a bisphenol of the formula below:

Lubricating oil

OH

Applicant:

"Shell" Research Limited, London

Representative: Dr. K. Schwarzhans

and Dipl.-Chem. Dr. phil. E. Jung, patent attorneys,

Munich 19, Romanplatz 10

Claimed priority:
Great Britain March 28, 1960 (No. 10 875)

John Atkinson, Kelsall and Keith Arthur Troth,

Vicars Cross, Chester (Great Britain),

have been named as inventors

The basicity of the metal naphthenates from Group II is used for the purposes of the present Invention defined by the formula

(f-l) 1000/0.

in which X is the radicals - S -, - S - S -, - Se -, -S-CH ₂ -, --CH ₂ -S —CH ₂ -, -C (H) R-, -C (R ₂ ) -, - (CHss) »- -NH-, - O- means, R is a methyl or ethyl group and η is an integer from 1 to 3.

The lubricating oils according to the invention are also suitable for diesel engines which are not completely have separate oil systems for the cylinders and bearings.

In this formula, M denotes the number of equivalents of the metal from group II and E denotes the number of equivalents of naphthenic acids in a certain amount of the basic salt.

The naphthenic acids used can be obtained from various petroleum fractions, and you can z. B. have average molecular weights in the range of 150 to 750. As a representative of Group II of the salt-forming metals are strontium, magnesium, zinc, barium and calcium called. The salts of barium and calcium are particularly preferred.

The basicity of the metal naphthenates should be higher than 400, preferably higher than 600, e.g. B. 800 or even be about it. Methods for the preparation of strongly basic alkaline earth naphthenates are well known, and they are used, for example, in British Patent Nos. 786 167, 790 471, 795 172 and 795 657 described. The preferred procedure for the preparation of the highly basic salts, which according to the The present invention is described in U.K. patent 786,167.

309 687/287

The strong base naphthenate can also be generated in situ in the lubricating oil (see British patents 795 172 and 795 657).

The strong base salt can also be made as a concentrate in a lubricating oil, which can then be diluted with a further amount of a lubricating oil.

The amount of highly basic Group II metal naphthenate which can be incorporated into the lubricating oil is e.g. B. 0.2 to 10% and ¹⁰ preference, from 0.5 to 5 weight percent, calculated on the weight of the base oil.

The alkylated bisphenols used in the lubricant blends of the invention are preferably those with a sulfur bridge or especially with a methylene bridge.

The alkylated bisphenols can contain one to eight alkyl groups; however, they preferably contain two to six alkyl groups. Alkylated bisphenols having four alkyl groups are particularly preferred. Each of the alkyl groups can contain 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms and in particular 4 carbon atoms. The alkyl groups of such a bisphenol can be the same or different, and ² S can be primary, secondary or tertiary alkyl groups. Bisphenols containing at least one tertiary alkyl group are particularly preferred.

Suitable representatives of the alkylated bisphenols to be used according to the invention are, for. B. bis (3-ethyl-4-hydroxyphenyl) disulfide, Bis (3-methyl-4 - propyl - 5 - hydroxyphenyl) disulfide, bis (2 - isopropyl - 3 - butyl - 5 - hydroxyphenyl) selenide, bis-1,2 - (2,6-di-tert-butyl-4-hydroxyphenyl) -thiaethane, 3 bis- (3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, 2,4-diisobutyl-3-hydroxybenzyl-2 ', 4 '-dipropyl-3-hydroxy- benzyl sulfide, bis-1,2- (3-octyl-5-tert-butyl-4-hydroxyphenyl) ethane, 1,2-bis- (2,4-ditert.pentyl-3-hydroxyphenyl) propane, bis (2 - tert. Butyl 5 - isopentyl-4-hydroxyphenyl) amine, Bis (3,5-dibutyl-4-hydroxyphenyl) ether.

The alkylated bisphenol with a sulfur bridge is bis (3-tert-butyl-5-methyl-2-hydroxyphenyl) sulfide and the alkylated bisphenol with a methylene bridge is bis (3,5-ditert.butyl-4-hydroxyphenyl) methane preferred.

The alkylated bisphenol can be prepared by any known procedure.

The alkylated bisphenols can be added to the lubricating oil before, during or after the incorporation of the highly basic Group II metal naphthenate. The amount of alkylated Bisphenol that can be added to the lubricating oil is 0.1 to 5% and preferably 0.5 to 2.5 percent by weight based on the weight of the base oil. The amount of alkylated Bisphenol, calculated on the weight of the highly basic naphthenate of a group II metal, can be 5 to 500% and preferably 10 to 150% by weight be.

The hydrocarbon lubricating oil can be a mineral one or a synthetic oil. The mineral oils are preferably essentially paraffinic and / or naphthenic. But you can also use substantial proportions of hydrocarbons aromatic structure. The viscosity can vary within wide limits, so that the oils for example SAE classes 5 W, 1OW, 2OW, 20, 30, 40, 50, 60, or 70.

The mineral oils can be mixed with synthetic lubricants, e.g. B. polymerized olefins, such as polyisobutylene, mixed or even completely replaced by these.

The lubricating oils can be blended with minor and acceptable amounts of fatty oils, such as bacon oil.

Other conventional additives can also be added to the lubricating oils according to the invention be e.g. B. rust inhibitors such as phosphorus-containing esters; anti-foaming agents such as silicone polymers; Detergents such as alkyl salicylates; Viscosity index improvers, such as polymeric acrylic acid esters; Extreme pressure additives such as dibenzyl disulfide; Rust preventers, such as the condensation products from maleic anhydride and long chain olefins; Oil improving agents such as non-acidic sebum and surface active agents Agents such as peroxidized aromatic extracts.

Both the basic metal naphthenates used according to the invention and those used alkylated bisphenols are known per se as lubricating oil additives. Bisphenols generally practice this only has a function as an antioxidant, d. That is, they have an oxidation-stabilizing effect. However, experience has shown that common known very strong antioxidants do not work are able to repair the wear and tear caused by the addition of naphthenate. Appropriate Comparative tests are given below. Surprisingly, however, occurs in the Concomitant use of the alkylated bisphenols considered according to the invention results in a great reduction wear, especially with bearings and cylinders.

In the following mixtures, which represent typical examples of mixtures according to the invention, the following oil mixtures are used:

Lubricating oil mixture A

a mineral lubricating oil with a viscosity of 650 seconds Redwood I at 6O ⁰ C 27%

a mineral lubricating oil with a viscosity of 170 seconds Redwood I at 6O ⁰ C 37%

Concentrate of a basic calcium naphthenate with a basicity of 1000 in a spindle oil (sulfated ash 8.5%) ... 36%

Lubricating oil mixture B

a mineral lubricating oil with a viscosity of 650 seconds Redwood I at 6O ⁰ C 7%

a mineral lubricating oil with a viscosity of 170 seconds Redwood I at 6O ⁰ C 57%

Concentrate of a basic calcium naphthenate with a basicity of 1000 in a spindle oil (sulfated ash 8.5%) ... 36%

Mixture I.

Lubricating oil mixture A and 1 percent by weight bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, calculated on the lubricating oil mixture A.

Mixture II

Lubricating oil mixture A and 2 percent by weight bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, calculated on the lubricating oil mixture A.

Mixture III

Lubricating oil mixture A and 1 percent by weight bis (3 - tert -butyl - 5 - methyl - 2 - hydroxyphenyl) sulfide, calculated on the lubricating oil mixture A.

Mixture IV

20th

Lubricating oil mixture B and 1 percent by weight bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, calculated on the lubricating oil mixture B.

Mixture V

Lubricating oil mixture B and 2 percent by weight bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, calculated on the lubricating oil mixture B.

Mixture VI

Lubricating oil mixture B and 1 percent by weight bis (3-tert-butyl-5-methyl-2-hydroxyphenyl) sulfide, calculated on the lubricating oil mixture B. Mixture IV and, for comparison, the lubricating oil mixture B were investigated in the manner described.

The results are given in the table.

For comparison purposes, lubricating oil mixture A is mixed with a selection of antioxidants and anti-corrosion agents other than alkylated bisphenols, namely with 1% zinc dithiophosphate, 2% zinc dithiocarbamate, 1% 2,6-di-tert-butyl-4-methylphenol, 1% thiophosphate and 2% phenyl α-naphthylamine, the percentages refer to lubricating oil mixture A as above.

Test method I

A Chevrolet o-cylinder gasoline engine is operated with constant high speed (3150 rpm) and 30 brake horsepower. In certain The engine was stopped at intervals to check the bearings. If the average The decrease in weight of the bearing over a period of 60 hours exceeded 200 mg considered the oil to be unusable in the context of the experiment.

Mixtures I, II and III according to the invention and, for comparison purposes, the starting lubricating oil mixture A, which contained the above-mentioned additives, were after the mentioned Method checked. The results are compiled in the following table.

Test method II

A 1 cylinder Shell Ricardo diesel engine was operated at 1500 rpm and 15 brake horsepower. After 160 hours, the crank bearings were checked and the weight loss determined.

Check
method lubricant Average
Weight loss of bearings I. Mixture I. 177 mg after 60 hours I. Mixture II 165 mg after 60 hours I. Mixture III 126 mg after 60 hours I. Lubricating oil mixture A Try + l% zinc dithio broken after phosphate 4 hours; camp unusable because of corrosion I. Lubricating oil mixture A 680 mg after + 2% zinc dithio 36 hours carbamate I. Lubricating oil mixture B 2000 mg after + 1% 2,6-diert. 32 hours butyl-4-methyl- phenol + 1% ter penthiophosphate I. Lubricating oil mixture A 573 mg after + 2% phenyl 3 hours a-naphthylamine II Mixture IV 14 mg after 160 hours II Lubricating oil mixture B 2737 mg after 160 hours

These results confirm that lubricating oil blends A and B, which are used as additives only contain basic naphthenates, give rise to severe wear, which is also not caused by the Use of known antioxidants is reduced to a sufficient extent. In the combined use of basic naphthenates and alkylated bisphenols are against it quite surprising improvements achieved.

Claims (9)

PATENT CLAIMS: 1. Lubricating oil based on a mineral or synthetic hydrocarbon lubricating oil, characterized by the content of a smaller proportion, preferably 0.2 to 10 percent by weight, calculated on the base oil, of a group II metal naphthenate known per se as a lubricating oil additive with a basicity above 400 and a smaller proportion, preferably 0.1 to 5 percent by weight, calculated on the base oil, of an alkyl derivative of a bisphenol of the formula known per se as a lubricating oil additive OH OH in which X is the radicals - S -, ■ —S - S -, oe, ο ^ rl2, v_Jrl2 ο i_-xl2, -C (H) R-, -C (R ₂ ) - - (CHa) ₇₁ -, - NH-, - O -, R is a methyl or ethyl group and η is an integer from 1 to 3. 2. Lubricating oil according to claim 1, characterized in that the metal naphthenate is derived is from a mixture of naphthenic acids with an average molecular weight in the range from 150 to 750, preferably 300 to 500, and that the metal is barium or calcium is. 3. Lubricating oil according to claim 1 or 2, characterized in that the basicity of the metal naphthenate is higher than 600, preferably higher than 800. 4. Lubricating oil according to claim 1 to 3, characterized in that the alkylated bisphenol has a sulfur or methylene bridge. 5. Lubricating oil according to claim 1 to 4, characterized in that the alkylated bisphenol one to eight, preferably two to six, alkyl groups contains. 6. Lubricating oil according to claim 1 to 5, characterized in that each of the alkyl groups of the alkylated bisphenol 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms contains. 7. Lubricating oil according to claim 1 to 6, characterized in that at least one of the alkyl groups of the alkylated bisphenol is a tertiary alkyl group. 8. Lubricating oil according to claim 1 to 7, characterized in that the alkylated bisphenol Bis - (3 - tert - 5 - methyl - 2 - hydroxyphenyl) sulfide or bis (3,5 - di-tert-butyl - 4 - hydroxyphenyl) methane is. 9. lubricating oil according to claim 1 to 8, characterized in that the amount of the Alkyherten Bisphenol in the hydrocarbon lubricating oil 10 to 150, preferably 20 to 60 percent by weight, calculated on the weight of the metal naphthenate. Considered publications:
German Patent No. 908 175; U.S. Patents Nos. 2,734U8, 2,791,559, 809 164; British Patent Nos. 786 167, 790 471;
French patents nos. 974 374,1 136 852, 1,148,986, 1,153,139.