DE1806899B2 - lubricant - Google Patents

Description

Distillation and / or dewaxing treatment sufficient for the production of the mineral lubricating oil. Even crude oils with a base of smell or highly aromatic crude oils which contain paraffinic hydrocarbons can be destroyed by refining measures well usable mineral lubricating oils are worked up. A polyolefin, for example a polyisobutylene, can be used. The viscosity Preferably contain the invention Lubricants also 0.01 to 2.0 percent by weight, in particular 0.05 to 1 percent by weight of a customary antioxidant, for example cajcium or zinc dialkyldithiophosphate, especially those Thiophobates, in which the alkyl groups are amyl and / or butyl groups. Even Alkylphenols, for example di- and trialkylbenols, preferably ^ o-di-tert-butyl - ^ - ineUiylphenol, and

The base lubricating oils can vary in wide ranges from alkyl bisphenols, such as bis- (3,5-dj-tert-butyl-4-hydroxyrene, and lubricating oils which phenyO-metban, are suitable for this purpose the SAE classes 5W, iOW, 2OW, 20, 30, 40, 50, 60 or 70.

The basic salts of naphthenic acid are expediently used in such an amount that they give the lubricating oil in a concentration of 1 percent by weight a potentiometrically measured total base number of 1.5 to 3 mg KOH / g.

The naphthenic acids in question may have an average molecular weight of e.g. B. 150 to 750 on ao sitätindex, z. B. polymeric acrylic acid esters, maximum ways. The excess basicity of the basic naphtha printing additives, such as dibenzyl disulfide, rust inhibitory acid salts, compared with the corresponding, for example condensation products from maggot neutral salts, is generally more than 400%, linic acid anhydride and long-chain olefins, medium preferably more than 600% and especially more to improve oiliness. than 800% up to the practically achievable highest as or surface-active agent, such as with peroxides be value. The aromatic extracts traded according to the invention are very suitable.

third class of antioxidants are arylamines such as phenyl-alpba-naphthylamine or phenylbeta-naphthylamine.

Other conventional additives can also be incorporated into the lubricants according to the invention, e.g. B, anti-wear agents, such as phosphorus-containing esters, antifoam agents, such as. B. silicone polymers, agents for improving the viscosity

Purposes barium, calcium, magnesium, strontium or zinc salts, with calcium salts being preferred. The excess basicities of the basic salts of naphthenic acids used according to the invention and aromatic carboxylic acids can be determined according to the following equation:

Excess basicity in%

100.

35

In this equation, M denotes the number of equivalents of group II metal and E denotes the number of equivalents of naphthenic acid or aromatic carboxylic acid per 100 g of the basic salt. The values for M and £ are chosen so that the lubricating oil at a salt concentration of 1 percent by weight has a potentiometrically determined total base number between 1 and 1.5 mg KOH / g.

Suitable basic salts of aromatic carboxylic acids barium, calcium, magnesium, strontium or Zinksake be suitably employed, wherein the Cal ^j ciumsalze are preferred. The aromatic carboxylic acids can be hydrocarbon-substituted benzoic acid, salicylic acid, dihydroxybenzoic acid, anthranilic acid or naphthocic acid. Examples of such acids are Ca-C ^ -alkylbenzoic acids, Ca-Cjj-alkylsalicylic acids and C _s -C ₂₂ -alkyl naphthoic acids, for example lauryl salicylic acids, stearyl salicylic acids or mixtures of C ₈ -C ₃₀ alkyl salicylic acids. Preferably ₁₄ -CjS * or C _l4 -C _Ä "alkyl * 53IiCyMuKn eingöäetzt be within the scope of the invention string of C. Such acids are conveniently used mustard for the preparation of mixtures of basic salts of C ₁₄ -C ₁₈ - or C ₁₄ -C _n -MonOaIkVl * and dialkylsalicylic acids. Particularly preferred is a mixture of tonic calcium salts of C ₁₄ -C ,, - Moüoalkyl- and DialkyUalicylsäufen. Such a salt minification is referred to below in the examples as salt * A «. Such salts expediently have ßbefschufibasitätsaten of 50, 200 or 600%.

The invention is illustrated by the following lubricants, some of which are merely serve for comparison.

Lubricant A (for comparison)

Weight percent

Basic calcramnaphthenate (800% Excess basicity) 5.0

An antioxidant containing sulfur and phosphorus 0.2

2,6-di-tert-butyl-4-methylphenol 0.2

Mineral lubricating oil with a medium viscosity index and a viscosity of 41 cSt at 6O ⁰ C remainder

Lubricant B (for comparison)

Basic calcium alkoxylates (Salt "A") (200% excess basicity) 4.0

Zinc amylbutyldithiophosphate as an antioxidant 0.2

Mineral lubricating oil with a medium viscosity index and a viscosity of 41 cSt at 6O ⁰ C remainder

Lubricant C (according to the invention)

Basic calcium alkyl salicylates (seeds »Ä4 '(2ÖÖ% © be« chußtJaSiaUä £) 3jö '

Basic calcium naphthenate (800% Excess basicity) 2.0

Zinc amylbutyldithiophosphate as an antioxidant 0.2

Mineral lubricating oil with a medium viscosity index and a viscosity of 4IcSt at 60 ^e C remainder

Claims (1)

Mt, m ^ '.-.- ui>: -'! ■ ·; -ν ■ · ■: - ■■ •• Lubricant - ή, <■ ■ 'ι.-Oberllicte yochjlost, r.-im- ■■ »ο 8er'.SO,. Auf-' mhmefn minutes. '··· '·'. 'Γ' - '. 1 ■ - ■ Iin-hours-2StoVieStd; A (Comparative 70 #' 110B (Comparative) C (Invention) 168. 1683.5 3.01.0 1.0730710 Test to determine the rust protection effect Dec percentage £ n.part of each rust-infected Qpepflachc dfes Prpbestiiclces is determined according to ASTM method D 665 using a 20 percent saturated salt solution as corrosive Mdi. Lubricant F (according to the invention), -π. Basic calcium alkyl salicylates (salt "A") (200% Excess basicity),. ,,.,.,. 4.0 basic calcium naphthenates (800% excess basicity) ........ 1.4 zinc amylbutyldithiophosphate as antioxidant ,, ....,. ,,, .. 0, 2 Mineral lubricating oil with a medium viscosity index and a viscosity of 41 cSt at 600C, the remainder Table II Test for determining the emulsifying power, the oil to be tested is in a device according to J ASTM method D 665 at 600C with 10 percent by volume of water stirred, and then allowed to sit at the same temperature under the influence of gravity. Samples are taken from the top layer after 2 and 16 hours, respectively, and their water spirit is determined. Determination of the oxidation stability This is a SCOT test at 1600C using an oil-soluble iron catalyst. From Table I it can be seen that a lubricating oil mixture which contains both basic calcium naphthenates and basic calcium alkyl salicylates has a particularly good rust preventive effect and good behavior when testing the emulsifying power and the oxidation stability. Lubricant D (for comparison) Percentage by weight of basic calcium alkyl salicylates (salt "A") (200% excess basicity) 5.0 Mineral lubricating oil with a medium viscosity index and a viscosity of 41 cSt at 600C, the remainder being lubricant E (according to the invention) Basic calcium alkyl salicylates (salt "A «) (200% excess basicity) 3.5 basic calcium naphthenate (800% excess basicity), 1.65 zinc ^ ylbutyldithiophosphate as a mineral lubricant with an average I / iskositltäindex and a yiskpsitlt of4I <& at * G .....:.,« / .. .. remainder »5A (comparison) evaluation of the piston cleanliness completely pure) jacket1 DHC JLubricantB (comparison) (10 = Rjng-webs5.8mgKOH / g30 D (comparison) grooves1,059,810.0C (invention) 0,54,93,95,0E (Invention) 5,04,38,86,25F (Invention) 5,84,09,77,83,73,49,78,05,15,98,06,4 *) Potentiometrically determined total base number. From Table II it can be seen in particular that the values for the total base number for lubricants C, E and F are greater than would be expected when considering the total base number for lubricants A, B and D. Thus, lubricants B and D correspond to a total base number of 1.25 mg KOH / g for a concentration of 1% by weight of basic calcium alkyl salicylates, and lubricant A corresponds to a total base number of 2 mg KOH / g for a concentration of 1% by weight of basic calcium naphthenates. This would give a total base number for lubricants C, E and F of 7.75, 7.675 and 7.8 mg KOH / g, respectively. In fact, however, Table II shows that the experimentally determined total base numbers are 7.8, 8.0 and 8.0 mg KOH / g, respectively. Furthermore, it can be seen from the above numerical values that the comparative lubricant A, which contains no more than Msisches naphthenate, achieves only a few KoibettreTniwites of i <5.5 or 18.2 or 22.0. 18 06 699 V 3) an ÖHösUchen basic salt, derived from an aromatic carboxylic acid, of a metal from group U of the Periodic Table of the Elements Lubricant, consisting of an atomic number from 12 to 56, given your Mmeralschmieröl and / or a syn- '4) oV up to 2.0 percent by weight of conventional antioxidant hydrocarbon lubricating oil, dating agents, in particular Z, nkd, 3lkylditb.o- 2) a phosphate derived from a naphthenic acid and / or 2> tert-butyl-4-methyl-oil-soluble basic salt of a metal of phenol, and givenraiis group II of the periodic table of the elements io 5) usual additives with an atomic number from 12 to 56,. . ". "Cai.Vnmnn" t, 3) one of an aromatic carboxylic acid is characterized in that it contains an oil-soluble basic salt derived as components 2 and 3 in combination 0.5 to 31 percent by weight mn-Metaüs of group II of the periodic table of the at least one of a naphthenic acid and 1 to elements with an atomic number of 12 to 15 6 percent by weight at least one of an aromatic-56, optionally matic carboxylic acid derived oil-soluble basic 4) 0.01 to 2.0 percent by weight of the usual anti-salt of a metal the group II of the periodic oxidants, in particular zinc dialkyl system of elements with an atomic number of 12 contains dithiophosphate and / or 2,6-di-tert-butyl- to 56, the potentiometer, certain 4-methylnhenol, and optionally ao total base number of the Lubricant 5_ to 12 mg 5) customary additives, thereby amounting to KOH / g, in particular 8 mg KOH / g. ke η η ζ eich η et that it was known as components, both oil-soluble basic salts 2 and 3 in a combination of 0.5 to 3 weight percentages of a naphthenic acid and oil-soluble basic salts percent of at least one of a naphthenic acid or petroleum sulfonic acid. a hydroxybenzoic acid and 1 to 6 percent by weight of at least 25 acid, such as salicylic acid, and using such proteins derived from an aromatic carboxylic acid as lubricating oil additives. The cheaply made oil-soluble basic salt of a gene naphthenate, however, does not show sufficient metal of group II of the periodic table effect with respect to z. B. the total piston purity of the elements with an atomic number of engines, while on the other hand the relative contains up to 56, whereby the potentiometric expensive salicylates the neutralizing effect, the adjusted total base number of the lubricant expresses as potentiometrically determined total base-5 to 12 mg KOH / g, in particular 8 mg KOH / g, number, not satisfied. amounts to. In this context, it was extremely surprising that when the components 2) and 3) identified above are used in combination in certain proportions, a synergetic effect is achieved which leads to a particularly favorable performance Lubricant, which is especially useful for those in engines without oil circulation. This results in motors that work without circulating lubricating oil. In large ship engines, part of the expensive salicylate is usually burned by the cheaper naphtha-heavy fuel oils, which can often be replaced with relatively large amounts of sulfur. When burning an increase in quality is connected. Sulfur dioxide and / or sulfur dioxide are therefore formed. The basic salts of naphthenic acid and trioxide as acidic combustion products; Corrosion problems in such tentiometrically determined total base number 8 mg ship engines can cause. Around which this amounts to KOH / g. To eliminate the potentiometric total base-induced difficulties or to keep the number, which is abbreviated to TBNE below, as low as possible, one has the 50 in question, according to ASTM method D 664-58 or according to lubricating oils, basic naphthenates of metals Method of the Institute of Petroleum No. 177/64 determined from group II of the Periodic Table of the EIe. The hydrocarbon products used as the base oil are added to neutralize the acidic combustion. Such lubricants can be based on mineral or synthetic origin, but not all of the requirements of the 55 leaps. It can be a single oil Praxis, in particular with regard to the anti-rust effect, or a mixture of oils. For example, the thermal stability and the basic own oil can include a mixture of mineral lubricating oils as the base oil. be put as a mixture of a distillate gas Lubricant of the invention: allows; lubricating oil and vain »bright stock«. On the other hand, * can remedy these disadvantages. 60 ah base lubricating oil but also a mixture of a mineral lubricating oil and a synthetic hydrocarbon lubricating oil can be used. The mineral 1) a mineral lubricating oil and / or a synthetic lubricating oil can be essentially paraffinic and / table hydrocarbon lubricating oil, or naphthenic character, but can 2} an oil derived from a naphthenic acid, also one with considerable proportions of aromatic Soluble basic salt of a metal from the group of hydrocarbons can be used. very II of the periodic table of the elements with a well usable mineral lubricating oil are made of high ' Ordinal number from 12 to 56, paraffinic crude oils obtained, t in this case is a