DE1794133A1 - Lubricating oils - Google Patents

Description

The invention relates to improved lubricating oils.
a dispersant additive based on substituted succinic acid ..- compounds with at least 50 aliphatic carbon atoms in the substituent.

In recent years it has been used by the lubricating oil industry
a new class of dispersant additives based on substituted succinic acids or their derivatives has been developed, the substituent of the succinic acids being im
possesses essential hydrocarbon character. In particular the setter, acidic ester, half-ester ·· Haibamides, acidic amides, amides, imides, amidines, amine salts and metal salts
substituted succinic acids, the substituent of which is a hydrocarbon radical or a radical with essentially carbon

109844/1418 _BÄD original

lenvas is hydrogen in character and is at least 50 aliphatic Containing carbon atoms, all diepersant additives for lubricating oils have found wide practical use.

In most internal combustion engines, these lubricating oil additives work in a more satisfactory manner without undesirable lifting effects Way. In some motor vehicle engines, however, it has been found »that when using lubricating oils that contain such additives on the metal surfaces of those parts of the engine on which water vapor condenses may, a mayonnaise-like sludge settles. For example Such sludge deposits were found in the valve housing covers and in the oil filler caps of these engines. Especially with smaller motor vehicle engines this sump formation occurs when using such Sohmler oils. Moisture from the ambient air can condense out on the named parts of the motors. Since these metals also come into contact with the lubricating oil, they form oil and the water in the presence of the succinic acid dispersant additive, the mentioned sludge deposits. Ea is of course required to have a possibility available to reduce this silt formation or deposition or to prevent completely.

It has now been found that the accumulation of sludge can be completely or at least largely avoided without impairing the dispersant effect, since one can Lubricating oils which contain compounds as dispersant additives / those of substituted succinic acids of the above

109844/1418 BAO ORlGSNAu

designated type are derived, demulsifiers for water-in-oil emulsions incorporated, This finding is surprising because it would be expected that such diemulsifiers the dispersant effect of the succinic acid dispersant additives counteract. For example, it is one of the reasons for the high effectiveness of this class of dispersant additives seen in the fact that they are stable wa3Ber-in-oil emulsions can form. With a demulsifier for water-in-oil emulsions should therefore actually cancel or largely reduce the effectiveness of the dispersant additive will. However, it has been found that these are demulsifiers effectively reduce or even completely prevent sludge formation, but still reduce the die-persant effect of the succinic acid derivatives.

The invention is therefore a lubricating oil with a Content of at least one dispersant additive derived from an oil-soluble substituted succinic acid compound, whose substituent contains at least about 50 aliphatic carbon atoms, which is characterized is that there is an additional 0.01 to about 5 parts by weight of a diemulsifier for water-in-oil emulsions.

Preference is given to the lubricating oils of the invention containing polyoxyalkyl mipolyols as demulsifiers "

The lubricating oils of the invention can contain from about 0.01 to about 5 weight percent demulsifiers based on the total weight of the lubricating oil composition.

109844/1418

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Are particularly preferred lubricating oils as Dispereant-to-Batz one of a substituted succinic acid of the type referred to above contain derived esters, acid esters, or a Halbester-half amide, acid amide, amide, imide, Araidin, amine or metal salt "As previously _t As previously mentioned, these compounds are a well-known class of modern dispersant additives.

The substituent of the succinic acids from which these are derived Disperaant additives derive is usually a saturated one or unsaturated aliphatic hydrocarbon freet, however, it can also carry aromatic groups or polar groups as substituents. The amber acid substances However, polar groups must not contain such high proportions that their hydrocarbon character becomes noticeable will be changed. Examples of polar groups are halogen atoms, keto, ether, aldehyde and nitro groups, as well as sulfur or groups containing sulfur and phosphorus. The maximum limit the content of polar groups is about 10% by weight, based on the weight of the hydrocarbon portion of the substituent.

The hydrocarbon radicals of the succinic acid dispersant additives should no longer contain about 5 olefinic bonds, based on the total number of carbon-carbon bonds. The number of olefinic double bonds should preferably not be higher than $ 2.

1098U / U18

BAD ORiGINAt

A suitable starting material for carbon substituents of the succinic acids, from which such DiS-persant-Zusätae derive are high molecular weight, essentially saturated petroleum fractions and essentially saturated polyolefins, in particular polymers of olefins with 2-30 carbon atoms, particularly suitable polymers derive from terminally unsaturated monoolefins, such as ethylene, propylene, butene ~ X, isobutene, hexene · !, octene-Ϊ, 2-Methylh.epten-1, 3 ~ C, cyclohexylbutene-1 and 2 - methyl ~ 5 ~ propylhexen-1. Polymers of olefins * whose olefinic double bond is not terminal are also suitable. Examples of such olefins are butene-2, pentene-2 and octene-4.

Copolymers of olefins, such as those above as Example mentioned, with other olefinically unsaturated compounds copolymerizable therewith, such as by an aromatic Residual substituted olefins, cyclic olefins, and polyolefins are also suitable. Examples of such Copolymers are isobutene *. Styrene », isobutene- ■ Butadiene, propylene-isoprene, ethylene-piperylene, isobutene-chloroprene, Isobutene - ChloroDren-, Isobutene - p-MethyIstyrol-, Hexen-1-Hexadiene-1,3- »Octeii-1-Hexen-1-, Hepten-1-Penten-1-, 3-methylbutene-1-octene-1, 3,3-dimethylpentene-1-hexene-1 and Isobutene— · Styrene * · Piperylene copolymers.

3) aa quantitative ratio of the monomer units derived from monoolefins to other monomer units in the copolymer affects the stability and oil solubility of those from such Kopolymarisaten produced end products. Because of

Oil-solubility and stability of .the substituted succinic acids are therefore intended to be aliphatic substantially saturated and substantially as copolymers, ie they are at least about 80 $> _t preferably about 95 wt .- ^ monomer units which are derived from aliphatic mono-olefins.

Specific examples of such as copolymers are a copolymerizate of 95 $> isobutene and 5 $> styrene, a terpolymer W of 98 $ isobutene, 1 $> piperylene and 1 # chloroprene, a terpolymer of 95 # isobutene, 2 i> butene-1 and 3 i> hexene-1, a Terpolyraerisat 80 # isobutene, 10 # pentene-1 and 10 36 octene-1, a copolymerizate of 80 36 hexene-1 and 20 56 heptene-1, a terpolymer of 90 $> isobutene, 2 36 Cyclohexene and 8 j6 propylene and a copolymer of 80 1> ethylene and 20 # propylene. The stated percentages relate to the weight fraction of the units derived from the monomer in question in the polymer, based on its total weights

Another source of suitable hydrocarbon substituents are saturated aliphatic hydrocarbons, highly refined high molecular weight white oils, or synthetic alkanes such as those obtained by hydrating the high molecular weight polyolefins described above or other high molecular weight olefinic compounds.

Preferred starting materials for the hydrocarbon substituents of the substituted succinic acid are polyolefins having a molecular weight of about 750 to about

w.: <_u ;, «, .., 109844/1418

BADORJGiNAL

10,000, in particular from about 750 to 5,000. It can also Polyolefins having a molecular weight of about 10,000 to about 100,000 and more, alone or in combination with polymers with lower 'molecular weight for the production of substituted Eernstein3 acids are used, from which sieve the lubricating oils contained in Λen according to the invention Have DispersEüit additives manufactured. These substituents higher molecular weight may also act as viscosity index improvers in the lubricating oils of the invention.

The kohlenwasserBtoffsubatituierten succinic acids can be prepared by known methods by reacting maleic anhydride with a corresponding olefin, polyolefin or a chlorinated hydrocarbon at temperatures of about 100 - produce 2OQ ⁰ C. The product obtained is a succinic anhydride with a large hydrocarbon substituent. The hydrocarbon substituent can also contain olefinic bonds which, if desired, can be saturated by hydrogenation. The anhydride can be converted into the appropriate by treatment with water or steam. ^ Dicarboxylic acid can be saponified. The anhydride is equivalent to the free acid in terms of its usefulness for the production of dispersant additives, such as are contained in the lubricating oils of the invention . Both the anhydride and the acid can be converted into the corresponding acid by reaction with a phosphorus halide or a phenol or alcohol by known processes.

1Q98U / U18

α * fl "

halide or converted to the corresponding ester.

Instead of an olefin or a chlorinated hydrocarbon can also be other hydrocarbons that have a containing activating polar substituents, i.e. a substituent that relates to the carbon hydrogen molecule activated by reaction with maleic acid or maleic anhydride, used for the production of substituted succinic acids become »Examples of such polar substituents Bind

Mercapto,
Sulphide, disulphides, nitro _r / keto or aldehyde groups or

Halogen atoms. Examples of such polar substituted hydrocarbons are polypropylene sulfide, dipolyisobutene disulfide, nitrated mineral oil, dipolyethylene sulfide and brominated polyethylene. Another suitable method for the preparation of substituted succinic acids or, Bernsteinsäureanhy ~ hydrides consists in with an olefin having a high molecular weight or a polar-substituted hydrocarbon in the reaction of Itaoonsäure! Temperatures may range from about 100 to about 200 ⁰ C. Similarly Chlormaleineäure or chloromaleic instead of Succinic acid, succinic anhydride or itaoonic acid are used

The reaction of polyolefin-substituted succinic acids or succinic anhydrides with mono- or polyamines, especially polyalkylenepolyamines with up to about 10 amino nitrogen atoms in the molecule are particularly well suited. This uneeteun product " usually contain amides, imides, amine salts, amidines or mixtures of the compounds mentioned, which react by reaction

(* £ ■■> ■ * -. * .. 109844/1418

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of amino ticket atoms with acyl groups of succinic acids develop. The reaction products of polyisobutenyl succinic anhydride with polyethylene polyamines, which are im Average of up to about 10 amino nitrogen atoms in the molecule contain, slnct particularly good dispersant additives, In the Usually the polyalkylenepolyamine with the acid or the Anhydride reacted in such a quantitative ratio that the reaction mixture is about 0.5 equivalent up to 2 moles of poly- ' amine per equivalent of acid. The conversion products from polyisobutenyl (750 molecular weight to about 1 100) succinic anhydrides with polyethylene polyamines, which in Burehsohnitt contain about 3 to 7 amino nitrogen atoms in the molecule, in an equivalent ratio of anhydride to amine of 1: 1, are particularly effective bispersant additives. ,

As already mentioned above, these diepersant additions are known to the person skilled in the art. For example, the reaction products of substituted succinic acids or substituted succinic anhydrides with amines are described in the following US Patents; 3,018,250, 3,024,195, 3,172,892, 3,216,936, 3,219,666 and 3,272,746. The dispersant additives derived from substituted succinic acids also include the products that are obtained by aftertreating a β reaction product of an amine and a substituted succinic anhydride with carbon disulfide, a boron compound! an alkyl nitrile, urea, thiournate, nianidine or alkylene oxides. Such products are, for example, in _{U.S. Patents:} 10S844 / U18

-ιοί 200 107, 3 256 185, 3 087 936, 3 254 025, 3 281 428, 3,278,550 and 3,312,619 and British Patent 1,053,577.

Metal salts of substituted succinic acids are described in U.S. Patent 3,271,310. Preference is given to the salts of metals from group I or II, aluminum, lead, tin, Cobalt, nickel or zinc.

Esters of such substituted succinic acids are also suitable dispersant additives. These esters are by reacting the substituted acid or its anhydride with a monohydric or polyhydric alcohol, phenol or naphthol prepared by the processes customary for the preparation of carboxylic acid esters. These esters can also be obtained by that one first esterifies maleic anhydride or itaeonic acid with an alcohol, phenol, naphthol or alkylene oxide and the esters obtained in this way are then treated with a chlorinated hydrocarbon or a polyolefin further converts the desired dispersant additives. Typical

Examples of such esters are given in the British patent

and the OAS 1 271 877

981 850, U.S. Patent 3,311,558 / besehrleben. The esters of polyolefin-substituted succinic acids or succinic anhydrides with polyvalent ones are preferred: aliphatic alcohols containing 2 to 10 hydroxyl groups and up to about 40 aliphatic ^ carbon atoms. Examples of such alcohols are ethylene glycol, glycerine, sorbitol, erythritol, mannitol, polyethylene glycol, diethanolamine, Trläthanolamin and I, N »-di (hydroxyethyl) -äthylendiaain.

109844/1418

§ASS ORIGINAL-

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If the alcohol amino nitrogen atoms with reactive Wasseretoffatomen.bzw. if an amine to be reacted with a substituted succinic acid contains reactive hydroxyl groups, the reaction product can of course be a mixture which contains both N- and O-acylated groups. Such Realctionsproduktgeniische can Halbester shark bamide, containing half amine salt semiamides half amine salt Halbester, esters and imides (see. Eg USA.-Patentßchrift 3342033) · _Ä

As both the Dlepersant additives and those containing additives Lubricating oils are known, can refer to the above-mentioned patents for further individual pages to get expelled. These references contain detailed information on the various dispersant additives the basis of substituted succinic acids and their production. Also in these publications Described lubricants containing such dispersant additives. Lubricating oils of this type are according to the invention improved.

The diemulsifiers suitable for the purposes of the invention should preferably be at least partially soluble in the base lubricating oil. The diemulsifiers. can be used in amounts of from about O ₁ eq to about 5 wt .- ^, based on the weight d «a finished Söhmieröl8 _f. One of the main advantages of the invention, however, is to be seen in the fact that very small amounts of dismulsifier are effective. In most cases, di-mulgator concentrations of about 0.01 to about 15 tons are sufficient

109 & U / U18

Usually 0.02 to about 0.5 wt
To achieve effect. This means that even diemulsifiers, the solubility of which is very low in the lubricating oils to which they are to be added, can be used without further ado and with satisfactory results.

Numerous commercially available demulsifiers can be used in the lubricating oils of the invention. For example, the commercially available "SAPAC" demulsifiers. Preferred "GAPAC" demulsifiers are the alkylphenoxy poly (ethylene oxy) ethyl mono and diesters of phosphoric acid, for example OAPAC HE-61Q and RE-960 Other suitable ones Dismulsifiers are the reaction products of various organic amines, carboxamides and quaternary ammonium salts with ethylene oxide. These polyoxyethylated amines, amides and quaternary ammonium salts are sold under the names "ETHODUOMEEN T / 20", an A'thylenoxydkondensationsprodukt of an M-Alkyialfcylenediamins, which is sold under the name DUOMEEN T ^! ben is, "ETHOMEEN * (tertiary amines, produced by the addition of ethylene oxide to primary aliphatic amines. ·)," ETHOMID "(ethylene oxide condensation products of fatty acid amides) and" ETHOQUAD ¹¹ (polyoxyethylated quaternary ammonium salts, such as quaternary ammonium chlorides).

Preferred demulsifiers are polyoxyalkylene polyols and their derivatives. Dismulsifiers of this type are commercially available under various names, e.g. Ö- "ilüRÖNIC POLYOLB "Polyglycol 112-2 (a liquid tri-oil, manufactured from ethylene oxide and propylene oxide) and "TERGiTOI"

1Q9844AU18

BATH ORIGINAL.

phenyl or nonylphenyl polyethylene glycol ether) and (Polyalkylene glycols and their derivatives). The above-mentioned demulsifiers are just a few examples of commercially available products which can be used for the purposes of the invention.

In addition to the polyols themselves, their carboxylic acid esters are also used suitable. Examples of suitable carboxylic acids for the production of • such esters are lauric acid, stearic acid, succinic acid ; Re and alkyl or alkenyl-substituted succinic acids, their alkyl or alkenyl radicals up to about 20 carbon ~ contain atoms.

Preferred polyols are produced as block polymers. For example, a hydroxyl-containing compound of the general formula R- (OH) _n , in which η is an integer from 1 to 6 and R is the radical of a monohydric or polyhydric alcohol, phenol or naphthol, is combined with propylene oxide to form a hydrophobic base polymer implemented, mn which then ethylene oxide is added to incorporate a hydrophilic part in the molecule, so that a polymer is obtained that contains both hydrophobic and hydrophilic residues in the molecule. The size ratio of these residues can be controlled by varying the behavior of the reactants used or the reaction time or other reaction conditions. Thus, the Paoüjc can easily produce polyols, so that molecules never expand hydrophobic and hydrophilic dimples in a ratio to one another , due to which, this

Products as demulsifiers for any SchmicrölgMdseh · are suitable, no matter what base oils these lubricating oils are and regardless of whether other additives are present. ,

If greater oil solubility is required for a particular lubricating oil mixture, then the hydrophobic one can be used Make the part of the molecule larger and / or the hydrophilic part of the molecule smaller. If a greater water-in-oil emulsion breaking effect is required, the achieve by matching the hydrophilic and / or hydrophobic parts of the molecule accordingly.

Examples of compounds of the general formula R- (OH) _n are alkylene polyols, such as alkylene glycols, alkylene triols and alkylene tetrols, for example ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol and mannitol. It is also possible to use aromatic compounds containing hydroxyl groups, for example alkylated mono- or polyhydric phenols and naphthols, such as heptylphenol or dodecylphenol «

Other suitable demulsifiers are the esters described in U.S. Patents 3,096,827 and 2,674,619.

Under the name ^"w PLUROHIC polyol su beeiehenden polyols and other similar PoIyöle are particularly well suited as de-emulsifiers. These" PLURONIC polyols "are of the general formula I

HO- (CH ₉ CHj) O) - (CHCH ₂ O) _v (CH ₂ CH ₉ ) _Ä -H

09SU / U It. ■ ..:

#AD

in which x _t y and ζ are specific numbers of more than 1, with the caveat that "the CH ₂ GH ₂ O groups make up about 10 to about 40% by weight of the glycol molecule" and that the average molecular weight is between about 1 000 and about 5 000 is *

These products are made by first making propylene oxide with propylene glycol to form the hydrophobic base polymer

condensed, this condensation product is then reacted with ethyl ether in order to graft hydrophilic parts onto both of the molecules. The best results are obtained if the units derived from ethylene oxide make up about 10 to about 40 wt .- ^ of the molecule. Products in which the molecular weight of the polyol 2500-4500 and the units derived from ethylene oxide and about 10 to about 15 wt -.% Make up the molecule, are especially overall 'is suitable. The poly oils with a molecular weight of about 4,000 and about 10 i> of xethylene oxide-derived monomer units in the molecule are very particularly suitable. . ,.

The lubricating oils of the invention can not only be used as baais oils Mineral oils but also contain other natural or synthetic oils. Examples of natural or synthetic base lubricating oils are the hydrocarbon oils that can be produced by polymerizing olefins those from alkylene oxides manufacturable oils. Synthetic ester oils, such as those made from polybasic carboxylic acids and alcohols, are also included Glycols and polyglycols divisible ester

109844/1418

oils are suitable as base oils for the purposes of the invention. Examples of such ester oils are dibutyl adipate, di (2-, ethylhexyl) sebacate and dilauryiazelate. As already mentioned above, the lubricating oils of the invention can contain other dispersant additives based on substituted succinic acids and the diemulsifiers as well as the dispersant additives necessary for the invention Contain additives. Examples, games such additives are aechehältige detergent additives, viscosity index improvers, pour point depressants, foam inhibitors _t Hochdruckausätze, rust inhibitors and Qxydations- and corrosion inhibitors.

Examples of detergent additives containing ash are oil-soluble, neutral or basic alkali or alkaline earth salts of sulfonic acids, carboxylic acids or organic phosphoric acids which have at least one direct carbon-phosphorus bond, such as those obtained by treating a polyolefin, e.g. polyisobutene with a molecular weight of 1,000, with a "Phoaphatierungamittel, for example phosphorus trichloride, Phoepborheptaeulfid, Fhoaphorpentasulfld, Phoephortrichlorid and sulfur, white phosphorus and a sulfur halide, or Dithiophoephorsäurechlorid, producible compounds * the salts of such acids most commonly used are the sodium, potassium, lithium, calcium, magnesium, Strontium and. Barium salts.

The term "basic salt" is used to denote metal salts used in which more than the

preserved organic Säurereaten sfcöchicraetrifiche Metallaenge contain int. The methods commonly used for the preparation of basic salts are that you ₀ a metal hydroxide, a Mineralb'llösung an acid with a basic metal compound, for example, hydroxide, carbonate, bicarbonate, or sulfide in the heated excess over the amount etö'chiometrische to a temperature of more than 50 ⁰ C and then the thus obtained Reaktiöns- ™ mixture filtered. It is also known to carry out this reaction in the presence of a "reaction promoter" in order to support the incorporation of a large excess of metal

Examples of suitable as a reaction promoter compounds are phenolic compounds such as phenol, naphthol, alkylphenols, thiophenols, sulfurized Allcylphenole, condensation products of formaldehyde with such phenolic compounds, alcohols such as methanol _f, Ieopropanol, Octylalko- _ hol / Ä'thylengiykolmonomethyläther Diäthylenglykolmono- ^ ■

methyl ether, ethylene glycol and cyclohexyl alcohol, amines such as aniline, phenylenediamine, phenothiazine, O ^ -phenyl-flnaphthylamine and dodecylamine, a particularly two-knot process for the production of basic salts consists in an acid with a basic alkaline earth metal compound in excess, a phenolic alkaline earth metal compound ee "ktlonsfOrd * r" r and a small amount of water mixed, and this mixture BTI elevated temperature, for example 60-200 ⁰ C, treated with carbon dioxide ·

109844 / U18

Examples of oil pressure additives, corrosion inhibitors and oxidation inhibitors and chlorinated aliphatic hydrocarbons, such as chlorinated paraffin wax, organic sulphides and polysulphides, such as benzyldilsulphide, bis (chlorobenzyl) disulphide, dibutyltetrasulphide, sulfuric acid, sulfuric acid, sulfated sperm oil , sulphurized dipentene and sulphurized terpene, phosphosulphurised hydrocarbons, väe the reaction product of phosphorus pentasulphide with turpentine or oleic acid methyl ester, esters of pboaphorous acid, mainly organic secondary and tertiary phosphites, tertiary phosphites, lipophosphite, lipophosphite, lipohexylphosphite, lipophylphosphite, lipophylphosphite, lipicophosphite, lipohexylphosphite, lipohexylphosphylphosphite, lipicophylphosphite, lipohexylphosphylphosphite, lipohexylphosphylphosphite, lipicophylphosphite, lipohexylphosphite, phenylphosphylphosphite, lipicophylphosphite, lipicophosphite, phenylphosphylphosphite, phenylphosphylphosphite, lipicophosphite, phenylphosphate, e.g. Dietearylphosphit _r Dimethylnaphthylphoephit, 01eyl- (4-pentylphenyl) "phO8phit, polypropylene (molecular weight 500) and ~ phenylphO8phit Diiaobutylphenylphoaphit, metal thiocarbamates, such as Zinkdioctyldithiooarbamat and ■. Bariumheptylphenyldit hiooarbamat that produced Dithiophosphoreäuresalze yon Group II metals such as zinc dicyclohexylphosphorodithioate, Zinkdioctyldithiophoaphat, Bariue-di- (heptylphenyl) -dithiophQ8phat, Cndniiumdinonyldithiophoephat and AXN Zinkaalz a Dithiophoaphorsäure by Uasetsen ▼ on Phoepiiorpentaeulfid with an equimolar mixture of isopropyl pan oil and n-HesylalJcohol is.

The soapy oils of the invention can furthermore contain metal-containing detergent additives in amounts of generally from about 0.1 to about 20 weight percent. For some areas of application, such as turning Sobiffsdisselmotoren, the lubricating ^ m? Z ₄ ^ 109844 / UI 8

3 / Φ ORJGlNAt

oils of the invention contain up to 30% by weight of a metal-containing detergent additive. Furthermore, they can contain high- _{viscosity additives r} viscosity index improvers and stop point depressants in quantities of 0.1 to about 10 wt.

The examples illustrate the invention. Unless otherwise specified, all percentages' refer to the. Total weight of the lubricating oil,

Greasy - A. .

By reacting a chlorinated polyisobutylene having an average molecular weight of 1,050 and a chlorine content of 4.3 # with maleic anhydride, a polyobutenyl succinic anhydride having an acid number of 105 and an equivalent weight of 540 is prepared. A mixture of 300 parts by weight of the Polyisobutenylbernstelneäureanhydride and 160 weight parts of mineral oil is carried out at 65-95 ⁰ C with an equivalent amount (25 parts by weight ·, "Polyamine H", a Äthylenamingemiech having an average composition corresponding to that of tetraethylene pentamine) were added. This mixture is then ^{heated to 150 0} C, iw da * at the. The waeeers formed in the action are sealed off. Among other things, the complete removal of the water is carried out by stickfitoff through the Geaie'ch. The residue is diluted bit 79 weight «share mineral oil. The oil solution has a stioketoff content of 1.6% by weight.

109944/1418

This product is incorporated into the lubricating oils according to the invention given below as succinic acid diepersant additive.

1. SAE 20 mineral beer oil with a content of OyS # of the bispereant described above and 0.2 $> of a polyoxyalkylene glycol of the general formula I given above with a molecular weight of about 4,000 and a content of about 10% by weight of ethylene oxide units Molecule.

2. SAE IOW-30 mineral lubricating oil with a content of 1.0 $ of the succinic acid dispersant and 0.3 % "GAPAC RE-960", ie an alkylphenoxypoly - (ethyleneoxy) - ethyl-mono- and "dieatergder phosphoric acid .

3. SAE 10 mineral lubricating oil containing 0.06 i "Polyglycol 112-2% ie a liquid" Tripi, däsr calibration of ethylene oxide and propylene oxide derived _f 2 i "doe Berneteinöäure-Diepersants, 0.07 Ί" Phoephor in the form of Zinkdiootyldithiophosphat, 2 % of a barium detergent ingredient (produced by neutralizing the modifiedUiMetsUiig · product from a polypropylene (molecular weight 2,000) with 1 mole of phosphorus pentasulfide and 1 mole of sulfur with barium hydroxide <g 3 t of a barium eulfonate ale Dete ^ - gent additive, produced by reacting a MinereA bleaching of a mahogany sulfon aurβ with barium hydroxide / ia 500 ^> igen öberechuee about the stüahioaetritobe men <e% /

in the presence of phenol ale fieaktioneförderer and B # - ■ act with carbon dioxide at 180 ⁰ Cr eowie 3 ί a · ΐ 109S44 / U18

■ - 'ÖAD ORIGINAU

■ - 21 -.

"UsätKlichen ashless Dstergent-Susatzes prepared by copolymerization of a mixture ouch 95 Qew. ~ T Methäcrylsäureaaeylester and 5 Sew .-- $ acrylic, • aaurediatbylaminoathylester. .

4ο SAE 80 MineralBChmieröl containing 2 jf> of succinic acid-di 3persants, 0.1 # phosphorus in the form of zinc di-nhexyldithiophosphat, 10 $ chlorinated paraffin wax with a chlorine content of 40 36, 2 # dibutyl ». 2 $ pententene, 0.2 $ oleic acid, 0.003 ^ of a acid inhibitor, 0.025 ^ of a pearling agent, .3 $> of a viscosity index improver and 1.0 ^ of that by the addition of Bcdecylsuccinic acid with a. Polyoxypropylene- ^ condensation product of pentaerythritol with an average molecular weight of about 600 produced esters as a demulsifier.

Scbmlerttl 3

- ■ ■ ■ · ^ ■■ · --- ■

SAB 10 W-3G Honeysuckle, containing 5> a »Bern- ■;" $

Steinäuredieperaant-Zueatsea, manufactured according to

USA patent 3,524,043 by implementing diethanoi- ^

amine atite of a polyobutenyl (molecular weight 1,100) - \ ■ bernateinoÄure and 0.5 j> * Polyol 112-2 ", ie a

Triol, which is derived from ethylene oxide and propylene oxide

3oh »i * rgl C ■"'■ \ ■ .. * '*'

SAS 10 W-40 Mintrmlschäieröl, containing 3 ^ of the In the '"< SchJiieriJlen (A) mthmltenen B« rat »in§Äure-l} iipereant» _f 5 %

409144/141

17-133

The U.S. Patent 3,331,776 ibemehriifcben-en Dl- «Entere from Polyieobute ^ l-CMol ^ ulsr ^ 1

Fläureanh |, ydride and pentaerythritol, as well as 0.06 §6 " Ir-101 ".

■■ -:, -: ■■; ■ " ^Λ ·. -. '■■ ■ · .- ■ * · χ-3ί3« ϊ <<>ϊ->' · ■. ■. ..Ι -The effect of the Dlsffiulgaforen contained in the lubricating oils of the invention is through the following conversion results are explained. The tests were carried out as follows:

The test engine (a 1964 Ford Falcon six-cylinder engine with a displacement of 2,786 approx.) Is operated in cycles according to the following work: 45 min. Load run with a speed of 2 500 rpm. and a performance of 31 braking horsepower .. During the test cycle, the blow-through gases are passed through a cooler, from which the condensate formed there is returned to the crankcase. The working cycle described above is repeated five times in succession every day (corresponding to an operating time of the engine of 13 3/4 hours), after which the engine is switched off for the remainder of the day (10 1/4 hours). This completes a one-day test run. The experiment is carried out on successive days, the longest duration being £ 5. The daily assessment consists in the assessment of the valve housing oil with regard to emulsion deposits according to a numerical scale.The test engine is modified to the effect that it is provided with a water cooling system for the valve housing oil, which helps its temperature by controlling the water flow at 40.6 -

109844/14 ^ 18

ORIGINAL

46.1 ° C is kept * The VentiX housing cover is each after a running time τοη 13 3/4 hours removed and visually judged. The evaluation of the valve housing cover in a straight line of emulsion deposits is based on a numerical scale from 10 - 1, with 10 indicating the highest possible level of cleanliness. Immediately after the evaluation, the valve housing cover unscrewed again when the test continued shall be.

109844 / U1 8

Lubricating oil

(a)

The emulsifier Art

Table I.

Dismulsifier rating at the end of each

quantity, * fouling day 1st day 2nd day 3 * day 4th day 5th day

none

Polyoxyalkylene polyoi . (Polyol 112-2J

0.02

5p 5

Ii - (D none - 5.0 4.5 - (2) Polyoxyalkylene polyol
(Pluronic L-IOl) 0.06 9.0 9.0 - * III- (l)
J 17 - (D none 0.06 . 5.5
9.5
3.5 4.0
9.0 __ » v-duronic Ir-XuIJ
none 0.06 8.0 6.5 Polyoxyalkylene polyol
(Pluronic L-IOl)

7.0

6.5

5.5

6.0

6.0

4.5

5.0

5.0 4.0 (to)

Α.) Each of the Sehmier oils I to IV is a typiachea mineral Sehmier oil, which is called Bernsteinaäure-Disperaant the reaction product of a polyisobutenyl succinic anhydride and a mixture Clay contains ethylene polyamines. The lubricating oils I-IV differ from one another the type and concentration of the additives it contains. Within a group of Lubricating oils, see B. of group I, the individual lubricating oils (1) and (2) differ, however only because a di-emulsifier is present in one pail and not in the other.

b) While the attempt is normally canceled on or on the 5th day, it was canceled on this day continued up to the 7th day. The evaluation on the 7th day is 3.5.

Claims (7)

1. Soothing oil with a content of at least one of an oil-soluble substituted succinic acid compound derived bispersant addition, whose substituent is at least contains about 50 aliphatic carbon atoms, characterized by the fact that it also contains 0.01 to about 5% by weight of a dispersant for water-in-oil emulsions contains « 2p lubricating oil according to claim 1, characterized in that g e k e η η ζ ei c, h net that it is a polyoxyalkylene polyol as a demulsifier contains. 3. Sohmieröl according to claim 2, characterized in that the dispersant additive is at least one reaction product of a polyolefin-substituted succinic anhydride with an alkylene polyamine, which is obtained by reacting the anhydride with the alkylene polyamine in a proportion of about 0.5 equivalent to about 2 Hol Alkylenepolyamine has been produced per Xqtuiyalent anhydride. 4. Lubricating oil according to claim 3, characterized in that the diepersant additive is at least a reaction product of a polyobutenylsuccinic anhydride with an inert polyethylene polyamine. 5. Lubricating oil according to claim 4, characterized in that g · k β η η «• wages t that it is a polyoxyalkylene polymer as an oil emulsifier contains, whose Moltklile ia 109844 / U18 ~ 26 - essentially of a hydrophobic part with the groups the formula - CH - CH ₂ O - .. ι ■ · CH ₃ and at least one hydrophilic part with groups of the formula -CH ₂ CH ₂ O-. 6. Lubricating oil according to claim 5 »characterized in that that it is a polyoxyalkylene as a demulsifier contains glycol. 7. Lubricating oil according to Anepruch 6, characterized in that that there is a polyoxyalkylene glycol of the general formula as a demulsifier R0 (-CH ₂ CH ₂ O--) _x (-CHCH ₂ O-) _y (-CH ₂ CH ₂ O-) _Z «H CH ₃ includes, in the x, y and ζ are integers, with the proviso that the -CHgCHgO-ßruppen about 10 to about 40 $ dee ™ MoIe- kulargewichte of glycols auemachen and that daa average smolekulargewicht of glycols from about 1 to 000
about 5,000. β. Lubricating oil according to claim 7, characterized in that the polyoxyalkylene glycol is about 10 to
contains about 15 6ew-j6-CH ₂ CH ₂ O-groups. 9 Lubricating oil according to claim 8, thus rewarded, that the polyoxyalkylene glycol has a thermoset molecular weight of around 2,500 - 4,000 owns « 109844/1418 BATH ORIGINAL A lubricating oil according .Anspruch 9, dadurchgek e η η ζ eigh r> et that the Polyoxye3.kylenglykol has a Durchachnittsraolekulargewicht of about 4- 000th 109844 / U 18