DE1520211A1 - Lubricant preparation - Google Patents

Description

Dipl.-lng-.Dipl.oec publ. .

DIETRICH LEWSNSKY monks * May 1 PATENT ADVOCATE - MI «fcH-Pa $ ing, Agrses-Bemauef-SWM2 1520211

Telephone 1 8139

THE LUBHIZOi, CORPORATION, Box 3057 Euclid Station, Cleveland 17, Ohio, U.S.A.

Sohmi determination

U.S. priority dated May 17, 1963 based on U.S. patent application 231,329

The invention relates to novel compositions and processes for their production. In particular, look at the Invention of hates, which are used as plasticizers, detergents, Anti-rust agents, emulsifiers and as additives to soothing preparations, fuels, hydrocarbon oils and power transmission fluids are useful.

When formulating lubricant preparations for use in internal combustion engine !! » in the case of transmissions, gears, etc., one has dealt with the deterioration of lubricating oils,

Case LP - 497 90982 9/1404

particularly mineral oils. The deterioration dee oils lead to the formation of products which are opposite the metal pipes with which the oil comes into contact, have a corrosive effect * The deterioration also leads to the formation of products which are calibrated with formation of sludge and luck-like deposits accumulate · These deposits cause the moving metal parts to get stuck and hinder their free movement. You are one The main cause of failure and premature failure of the device that lubricates the oil.

It is known that water is a common contaminant Crankcase of an engine 1st. Ss canoe from the Decomposition of the cutting oil originate, or from the combustion chamber kobiuen as a blown product of combustion of the fuel »The presence of water in the lubricant seems to be the deposit of a raayonnaise-like calamwe to promote. This Schlawmart is more objectionable because it adheres tenaciously to metal surfaces and cannot be removed by oil filters. When the engine is in such conditions ijefaiiren that the temperature of the crankcase abrasive means is continuously high, the water is removed about as much as it accumulates and it is formed only a very small amount of the raayonnaise-like üchlararaea. On the other hand, when the temperature of the crankcase ventilator is alternately high and low or correspondingly low, water accumulates and a substantial amount

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Amount of the iaayoruiai β eähnli chen sludge is deposited in the engine.

High working temperatures are characteristic of a machine which consistently runs at a relatively high speed «Where, however, a motor vehicle arrives in the first line for exits fcurssen distances are needed as they are in city traffic and trips from home to work are characteristic, a notable part of the work is done before the Engine has reached its optimal high temperature. Bs will such an ideal environment for the accumulation of water in the Lubricant reached »There is a problem with this way of working mayonnaise-like Schiamma particularly disturbing. The solution to the The problem has come closer through the use of cleaning agents such as ketallphenolaten and -sulfonaten im Lubricants known to be effective in reducing engine deposits, which in work primarily at high temperatures. Unfortunately, such well-known detergents are not particularly effective in solving the problems associated with working at low temperature, especially problems related to treatment belyeliäuaeschmieramittel occur in machines, which at low or alternating high and low Te »; eraturate be driven.

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Accordingly, one of the main objectives of the invention is novel masses su create which for use as additives in Hydrocarbon oils and / or in lubricant preparations are useful or effective. Another object of the invention is the creation of hates that act as detergents (Detergents) are effective in lubricant formulations which are intended for use in engines that are used at low or work at intermittently high and low temperatures. Another aim of the invention is to create a method for Manufacture of additives, which are used as additives to hydrocarbon oils and lubricant preparations usable srlnd « Still another object of the invention is the creation of lubricant formulations and of fuel preparations.,

These and other objects are achieved according to the invention by Creation of a process for the production of phosphorus-containing seters, which is characterized by the reaction of one mole of a polyhydroxy compound of the formula:

R (OH) _x ,

In which R is a Kohienwaaserstoffradlkai and χ is an integer greater than 1, with about 0-5 to χ mol of an acid-producing mixture of (A) a succinic acid-producing compound from the class of hydrocarbon-substituted succinic acids and their halogens, esters and anhydrides, which have at least about 50 aliphatic carbon atoms in the

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Coal / asaersto / fsubatituenten? and (B) a phosphox

Self-acidifying compound of the class Phos ~ ph-ora acids, phosphorous acids and their halides, esters and anhydrides, where the molar ratio of the

hlti /

acid-producing compound and phosphorus / siture-producing Compound is within the range of about 0.1: 1 to 10: 1.

2ü the polyhydroxy compounds, of which the erfindungsgeraäsaen Phosphorus-derived esters include mainly polyhydric alcohols and polyhydric phenolsο They preferably contain less than about 30 carbon atoms. The polyhydric alcohols are particularly useful with about 2 to 12 carbon atoms and 2 to about 10 hydroxy radicals, preferably with 3 to 6 hydroxy radicals. Examples are alkylene glycols and poly (oxyalkylene) glycols like ethylene glycol, di ~ (ethylene glycol) »tri (ethylene ~ glycol), di (propylene glycol), tri (butylene glycol), penta- (ethylene glycol) and other poly (oxyalkylea) glycols which are produced by the condensation of 2 or more moles of ethylene glycol, Propylene glycol, octylene glycol or similar glycols with up to about 12 carbon atoms in the alkyl are formed enr ad ikal will. Other useful polyhydric alcohols include glycerine, pentaerythritol, 2,4-hexanediol, pinacol, Erythritol, arabitol, sorbitol, mannitol, 1,2-cyoloheiandiol, Xylyiene glycol and 1,3.5-cyolohexanetriol. Examples of multi-valued Phenols are hydroquinone, resorcinol, 4-heptyl-1,2-dihydroxybenzene, 1,2-dihydroxynaphthalene, 4-polypropene from

909 8 2 9 / UÜ4

Molecular weight 1500 substituted 1,2-dihydroxybenzene, 5 ~ methyl ~ 8-decyl ~ 1,2-dihydroxynaphthalene and pyrogallol.

Still other polyhydroxy compounds include the monoesters of the ölycerina, üorbits, Mamiits or other higher polyvalent ones Alcohols such as glycerol monoacetate, sorbitol monooleate, Mannitol monopropionate or the like. The copolymers can also be used an unsaturated alcohol with a copolymerizable one olefinic substance such as styrene, vinyl ether, vinyl acetate, isobutene, butadiene, divinylbenaol or the like. The copolymers contain 2 or more monomeric units, which are derived from the unsaturated alcohol are and thus form the for use in the invention Process provided polyhydric alcohols. Specific examples of such interpolymers are the copolymer aua 5 moles of allyl alcohol and a MoX styrene with an average molecular weight of about 2500.

The term "hydrocarbon" as used to describe the radical R in the formula of the polyhydroxy compounds is used, referred to in the present specification

a radical which, by its nature, is essentially approx

^ Is hydrocarbon. The radical can therefore be inert polar

K) Groups include provided that such groups do not

■ ^ are available in sufficiently large quantities »to keep the coal ^ waseeratoffciiarakter of the radical in a remarkable way to change. The polar groups are, for example, chlorine, bromine, keto, ether, aldehyde, nitro, etc. The upper limit

radically with respect to the amount of such polar groups in a hydrocarbon is usually about 10 ^ 6, based on the weight dee hydrocarbon radicals parts dee. In the case of Xther groups such as hydroxyalkylene or poly (oxyalkylene) groups, however, the radical can contain as much as one oxygen atom for every 2 carbon atoms

The hydrocarbon-substituted succinic acid-generating compounds which are useful for preparing the phosphorus-containing esters can be the succinic acids, anhydrides, halides or esters, some of which contains at least about 50 aliphatic carbon atoms. Sources of the hydrocarbon substituent include primarily the high molecular weight, essentially saturated petroleum fractions and essentially saturated olefin polymers, particularly polymers of monoolefins having from 2 to 30 carbon atoms. The particularly useful polymers are the polymers of 1-monoolefins such as ethylene, propene, ₈ -butene, isobutene, 1-hexene, 1-ootene, 2-methyl-i-heptene. 3 ~ cyelohexyl-1-butene and 2-methyl-5-propyl ~ 1-hexene. Polymers of medium olafins, ie of olefins in which the olefinic bond is not in the end, are also useful. They are illustrated by 2-butene, 3-pentene and 4-ootene.

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Also copolymers of olefins such as those mentioned above with other polymerizable olefinic substances such as aromatic olefins, cyclic olefins and polyolefins are useful. Such copolymers include for example those which are made by polymerizing: isobutene uit styrene, isobutene with Butadiene, propene with isoprene, ethylene with piperylene, isobutene with chloroprene, isobutene with p-methylstyrene, 1-hexeti with 1,3-hexadiene, 1-octene with 1-hexene, 1-heρten with 1-pentene » 3-methyl-1-butene or 1-octene, 3,3-dimethyl-1-p "nten with 1-hexene, isobutene with styrene and piperylene, etc.

The relative amounts of the monoolefins to the other monomers in the copolymers influence the stability and the oil solubility of the end products derived from such copolymers. Therefore, for reasons of oil solubility and stability, the copolymers provided for use in this invention should be essentially aliphatic and essentially saturated, ie they should contain at least about 80, preferably at least about 95 units, which differ from the aliphatic Derive monoolefins and contain no more than about 5 * of olefinic bonds, especially on the carbon-to-carbon covalent bonds. In most cases the prosentic content of olefinic bonds should be less than about $ t the total amount of carboniferous co-talents. ^ _{0 0RIGJNAL}

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Specific examples of such Hischpolyjnsrisate the copolymers of suhlen (based on weight) 95 ',' isobutene with 5 / "styrene, the terpolymer of B & fi Iaobuten with Υ, Ό piperylene and I ^ chloroprene terpolymers of 9i> V» isobutene with 2; 1-butene around % 1-hexene, the terpolymer of QiX * isobutene ta! T 10 · / »1-pentene and 10 $ 1-octene, the copolymers of 805i 1-hexene and 20i * 1-heptene, the Terpolymers of 905 * isobutene with 2 *, "Cyolohexene and S ^ propene, and the copolymer of 80 $ ethylene and 20 ^ propene.

To another. The source of the carbon dioxide radicals includes saturated aliphatic hydrocarbons such as high-molecular-weight olefinic, colorless, paraffin-oil-heavy or synthetic alkanes, but can be obtained by hydrogenation of the high-molecular-weight olefinic polymers or high-molecular-weight olefinic substances.

The use of olefin polymers having molecular weights VQA about 50 to $ 000 is preferred. It has been found that higher molecular weight olefin polymers of from about 10,000 to about 1,000,000 or greater impart viscosity index improving properties to the final product of the invention. The use of such higher molecular weight olefin polymers is often desirable. It should be noted that data dtr coal

909823 / UCU

hydrogen substituent in the succinic acid-sucking compound can also contain inert polar groups. He can in this ^ti insioht be a radical which carries essentially Kohlenwasserstoffoharakter, as in the above description of the hydrocarbon radicals R of the polyhydroxy "

The succinic acid neutralizing compounds useful in the above process are preferably essentially hydrocarbyl substituted succinic acids and anhydrides. These sucoin compounds are easily accessible from the reaction of maleic anhydride with a high molecular weight olefin or a chlorinated hydrocarbon such as the olefin polymer described above. The reaction consists in the mere heating the two reactants at a temperature of about 100 to 20O ⁰ C. The reaction product is a AlkenylhernsteinsUureanhydrid. The alkenyl group can be hydrogenated to the alkyl group · The anhydride can be through

to / treatment with water or steam of the corresponding acid be hydrolyzed. By reaction with, for example, phosphorus halide, phenols or alcohols, both the anhydride and the acid are converted to the corresponding acid halide or ester.

Instead of olefins or chlorinated hydrocarbons

can be found in the preparation reaction illustrated above the sucoin compounds use other hydrocarbons,

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■■ · ("■■ 'ψ

- 11 -

which contain an activating polar substituent, ie a substituent which is capable of activating the hydrocarbon molecule with respect to reaction with maleic acid or anhydride. Such polar substituents are, for example, sulfide, bisulfide, kitro, mercaptan, bromine, ketone or aldehyde radicals. Examples of such polar substituted hydrocarbons include polypropylene sulfide, bipolysobutene sulfide, nitrated mineral oil, high-density polyethylene sulfide, brominated polyethylene, etc. Another method which can be used for the production of succinic acids and anhydrides is the reaction of itaoonic acid with a high molecular weight olefin or a "polar-substituted hydrocarbon at a temperature usually in the range of about 10O bie ⁰ O ⁰ O is about 200.

Bio acid halides of succinic acids can be produced are caused by the conversion of the acids or their anhydrides with a halogenating agent such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride. I pray for such acids can be prepared simply by reacting the acids or their anhydrides with an alcohol or a phenol oil Compound such as methanol, ethanol, octadeeanol, cyclohexanol, Phenol, maphthol, ootylphenol ttaw. The teresterification is g - wähnlioh promoted by using an alkaline Catalyst such as Hatriujshydroxyd or I * trlue * lkoholat, or an acid catalyst · such as sulfuric acid. Bie Iat «r des alcoholic bsw. of the phenolieohen part of the prayer radicals

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seems to have little effect on the usefulness of tine · such Esters ale reaction * participates * in the above-described Frosees to have.

The reactants which can be used in the above process for the formation of the "invented phosphorus-containing beers" can generate phosphorus-containing acid * acids such as "anhydrides, udders or halides" an that is, those which contain both oxygen and sulfur. Therefore, "a phosphoric acid" is to be understood as a generic term to denote the class which includes phosphoric acid (R * PO ^) _t tetrathiophoephoric acid (H »P3.), MonotMophoephoric acid (H» PO, 3), bithiophoephoric acid (H ₅ PO ₅ S ₂ ) and frithiophoephoreic acid (H «F03 ·). It should be noted that acids, which contain both oxygen and sulfur, can further be characterized by the manner in which the oxygen or sulfur is attached to the phosphorus atom of the acid. The nomenclature used here essentially follows that used by American Chemical and Engineering Hew ·, Volume 30 »Vr. 43, October 27, 1952. According to this hone nomenclature there is, for example, a monothiophoephoric acid in which the sulfuric acid is only chained to the phosphorate (ie -P (S) (OH)), a shion phosphoric acid, whereas its isomer, in which the sulfuric acid is linked to both the

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Phosphorate "al · also an" In Wasseratoffatoa an & w links let (ie -P (O) (SH)), unites Kiiolpfcoephoreättre. is, the refusal of the floanalogues is only permitted if this homenclature is used, and the apesific names such as diootylphoaphoric acid and diphenylphoaphorigo acid ”only consist of oxo compounds, that is, (0otyl-O ₂ P (0 ) (0H) bew. (Ootyl ^ GPOH. Veranaohauliohend aei also basked, daee ^w phosphoric acid and Thioeäuren "" phosphoric "the oxy H FO. describes, whereas" be "know · How umfaaaen the DiaUcylphoephoreäuren, ie the DiaUcyleeter the Fhoaphoraäurens Dialicylphoephorsäure ( (AlJCyX-O) ₂ P (O) (OH) ₉ dialkyltetrathiophoephoric acid ((Al) CyI-S) ₂ -P (S) (SH)), OO-dialkyldithiophoaphoreic acid ((AlJCyI-O) ₂ P (S) (SH )), OS-dialkyldithionophoraic acid ((alkyl-0) (AIkJl-S) PiS) (OH)), O.S-dialkyldithiolphoaphoraic acid ((A13cyl-0) (alkyl-S) P (O) (SH)), OS -DiaUcyltrithiophosphoraäure ((A13cyl-O) (Alkyl-S) P (S) (8H)), etc.

For the production of the phoophore-containing sater according to the invention aind the anhydrides, seters and halides of those containing phoaphor Acid can also be used. The anhydrides of the phosphoric acids are particularly mentioned. They are veranaohaulioht by Phoephorpentoxyd, Phoephorpentasulfid, Phoephorheptaaulfld, Phoephoreesquiaulfid and Phoephoroxyeuifid. Examples of the anhydrides of organic phosphoric acids are the anhydrides of diphenylphosphoric acid and the like. To the halides of the phosphoric acids

909829 / U04 bad ORiGiNAU

For example, phosphorus trichloride, phosphorus pentahloride, thiophosphorus chloride, phosphorus tribromide, diphenylphosphorus chloride, 0.0'-S (chlorophenyl) thiophosphorus chloride, 0.0'-diphenylthiophoapherchlorld and diphenylphosphorus triochloride.

The esters of the phosphorus acids can be the completely esterified acids or the esterified acids. The latter are also known as acidic cats, ie at least part of the acid is not esterified. They are illustrated by the mono- or di-esterified phosphoric or phosphorous acids. The rating can be derived from a carbon atom, usually from one which has less than about 30 and preferably about 1 to about £ 4 aliphatic carbon atoms The hydrocarbon radicals can contain inert polar groups as described above. Examples are methyl, xthyl, chloromethyl, o-chlorophenyl, p-] 3romophenyl, ₉ OC-chloronaphthyl, B-eeptylnaphthyl, op-diaethoxyphenyl, tolyl, isobutyl, octadeoyl , 4-chloro-2-heptadecyl, eicosyl, caphyl, benzyl, chlorobensyl, 2-phenylethyl, cyclohexyl, cyclopentyl, 2-methylcyclohexyl, the hydrocarbon radical derived from foIypropen with a molecular weight of 1500, that of polyisobutene with a molecular weight of 5000 derived hydrocarbon radical, behenyl, stearyl, oleyl, allyl, propargyl, o-heptylphenyl, 2,4.6-trinethylphenylv 2-meroaptophenyl _f m-nitrophenyl , Methoxytetra-

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ethoxy-methyl, IO-keto-1-octadeoyl rom with polyisobutene of 1000 molecular weight substituted phenyl "xenyl, 5-Haphthyl-2-decyl, 10-Toly] r1-8tearyl and 9-10 MohlorstearylradiJcal ·

The commonly used esters are, for example, phosphoric acid methyl ester, phosphoric acid diethyl ester, phosphoric acid trimethyl ester, the O-methyl ester of thiolphoaphoraic acid, the dicyclohexyl ater of phosphoric acid _9, the O.O'-dioyclohexyl ester of dithiophoaphoric acid, the tetraphylohexyl dicyclohexyl ester of phosphoric acid -S-decyleeter of monothiophoaphoric acid »the O.O'-diphenyleater of monothiolphosphoric acid, the triphenyl ester of phosphorus acid, the triphenyl ester of phoaphoric acid» the tritolyl ester of phoaphoric acid, the mootadecyl ester of phosphorous acid, the trinaphthyl ester of phosphorous acid, the OO * -Binaphthylester of Monotiiionphoephorsäure, the O.O'-Dinaphthylester of Thiolphoephoraäure, the Di (heptylphenyl) ester of the phosphoric acid, the bia- (Uichlorphenyl) eater of the phosphorous acid, the S-Ben * ylester of the Monothiolphosphorsäure, the S. S'-diiphenyläthylJeater of dithiophosphoric acid, the OS-didecyleate he of the trithiolphosphoric acid, the S.S'-didodecyl ester of the trithiolphosphoric acid, the diphenyl ester of the tetrathiophoaphoretic acid, the O-dodecyl-S-phenyleater of the monothiolphophoric acid, the O.O'-biieooctyl ester of the dithiophosphoric acid, the di (nitrophenol of the phosphoric acid, the di (nitrophenol) ester of the phosphoric acid. 0 * -Di (nitrophenyl) eater of dithiophosphoric acid, of 0.0'-di (oethoxyphenyl) eater of

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Dithiophoaphoraic acid, the 0.O'-Di (methoxyphenyl) eater of dithiophoephoric acid, the 3) i (heptylphenyl- (OC ₂ H ^) ₂ o) ^{eBter deP} Phoaphoraic acid, the M (methyl- (0-O ₅ H ₇ -) ₁₅ ) eater of phosphoric acid, the deeyl-ootadecyl ester of phosphoric acid, the di (4-keto-1-deoyl) ester of phosphoric acid, the di (polyisobuteneMolecular weight 1500) -substituted phenyl) eater of phosphoric acid, the 0.0 * -di (polypropene ( Molecular weight 300) -substituted haphthyl) eater of dithiophoaphoric acid, and the oleyl ester of phosphoric acid.

The seters of phosphoric acid and thiophoaphora acids are obtained by the reaction of phenol or an alcohol with phosphoric acid or a thiophosphoric acid or an anhydride of the acid such as phosphorus pentoxide, phosphorus pentasulphide or phosphorus oxysulphide. The reaction is usually carried einfachea mixing the reactants at a temperature above about 5O ⁰ C, preferably between about 80 and 150 ⁰ C is performed. In many cases, however, the esters of phosphoric acids tend to be at high temperatures to zersetzenο Therefore, it is often desirable to provide a longer Sinwirkenlassen of temperatures above about 15O ⁰ C to the Reaktionegemisch to vermeidenο Hau can be used in the reaction, a solvent to the mixing to facilitate the reaction participants and to control the reaction temperature. " The solvent can be benaol, naphtha, chlorobenzene, mineral oil, kerosene, cyclohexane, or carbon tetrachloride. A solvent which is able to interact with water relatively

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low-boiling azeotropic Gemisoh "u form" also contributes sur removal of water in the esterification of an alcohol or phenols with the reaction participant of the phoaphorhaltlgen Acid at ο The relative amounts of the alcohol - baw · phenol participant θ and the acid reactant influence the texture of the obtained estera · For example, tend equimolar amounts of an alcohol and phosphoric acid to bring about the formation of a monoester of phosphoric acid, where-

however, the use of a molar excess of the alcohol reactant in the reaction mixture tends to reduce the proportion increase in diesters or trieaters in the product

Cases the product becomes a mixture of the mono-, di- and tri-ethers

is * the acid and e% n such a mixture of economic

Reasons desired for use in the present invention

The reaction of an alcohol or phenol with phosphorus penta ~ sulfide usually leads to the O.O'-diester of the dithiophoe-

'm.

phoric acid, Sine such reaction involves 4 moles of the alcohol or phenol per mole Phosphorpentaaulfid and can be carried out within the temperature range of about 50 ⁰ O au to about 250 ⁰ C. Thus, the preparation of 0.0 * di-n-hexyldithiophosphoraäure in the reaction of Phoaphorpentasulfid with 4 moles of n-hexyl alcohol at about 10O ⁰ C for about 2 hours. Hydrogen sulfide is released and the residue is the defined acid. Treatment of phosphorodithioic acid with water or steam removes one or both of

909829/1404

atone lind converts the product into the corresponding monothlophosphoric acid or phosphoric acid.

The compounds of tetrathiophosphoric acid can be prepared by a first reaction of a mercaptan or thiophenol with PSOl. or PSBr, to form an intermediate which is either a Trithiophosphorhalogenid or Trlester the! Petrathiophosphorsäure _t 1st, and the subsequent reaction of the intermediate with hydrogen sulfide or Hatrlumhydrosulfld "Ester the Trithiophoephoraäuren be obtained by treatment of esters of Tetrathlophosphorsäuren with water or steam.

The esters of phosphorous acids are obtained by the Reaction of an alcohol or phenol with phosphorous acid or a phosphorus trihalide such as phosphorus tribronide or phosphorus trichloride and the reaction noted above Usually carefully controlled conditions such as low temperature to allow a substantial yield of the setter of phosphorous acids gives «Under other conditions the reaction of an alcohol or phenol with a Phosphorus trihalide lead to a phosphoric acid or Beter. Such esters are easily subject to rearrangement to form phosphonic acids and esters.

The reaction by which the phosphorus-containing esters of the present invention are obtained can be easily effected

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- 19 -

by mixing a polyhydroxy reactant «old the succinic acid-producing ones and the phosphorus-containing ones acid generating reactants at the desired temperature. The use of an inert solvent the reaction is not necessary, but is often desirable, especially if a highly viscous or solid reaction »» Participant in the reaction mixture is · Bas at the Inert solvents that can be used for the reaction can be a hydrocarbon such as benzene, toluene, naphtha, cyclohexane, η-hexane, or mineral oil.

The reaction by which the phosphorus-containing esters according to the invention are obtained was carried out by adding the polyhydroxy compound, the hydrocarbon-substituted, succinic acid-producing compound, and the phosphorus-containing acid-producing compound at a temperature! " r above about 10O ⁰ C, preferably between about 125 and 250 ⁰ C mixes. The optimal reaction temperature will depend to some extent on the nature of the particular reactions used. Are acid anhydrides, the reaction temperature can be below about 20 ° C. On the other hand, when the acid generating reactants are esters such as diraethyl esters of hydrocarbyl-substituted succinic acids and triphenyl esters of phosphoric or phosphorous acids, the reaction temperature often becomes

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20O ⁰ C or higher leg. The maximum limit for the process is determined by the decomposition point of the reaction chemistry. Sr overalls 300 ⁰ C seldom

Bas calibrated from the method according to the invention The product is usually a complex mixture of esters, which aioh from the polyhydroxy reactant through the Esterification of some of its hydroxyl groups with the succinic acid generating one Compound, and the esterification of some other hydroxyl groups with the phosphorus-containing acid-generating ones Connections derives. This is how it is according to the invention Product a complex mixture of esters, characterized by the presence of both ester radicals of the amber acid ester type, as well as the ester type of phosphoric acid, ^ ie the exact composition of the Product is not entirely clear. Accordingly, it can be Best describe the product by the process by which it is made.

The composition of the product according to the invention depends mostly on the relative amounts of those used in the process three respondents. For reasons of usability and the stoichiometry of the esterification, the Total amount of succinic acid-sucking reactants and phosphorus-containing β-acid-producing reactants, which per mole of the polyhydroxy reaction participant are to be used, usually in the range of about 0.5 moles

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up to β ο vi el moles like the Ansah! the hydroxy radical inside · » half of the molecular structure of the polyhydroxy reaction participant. Pemer are the relative amounts of succinic acid generating Reactants and phosphorous acid-generating reactants usually in such a way that because they are in the range of molar ratios of about 0.1: 1 ssu are about 10x1. Be reactions with a mole of one Tetrahydroxy compound, such as pentaerythritol, can be a mixture of succinic acid-generating reactants and Apply phosphorus-containing acid-generating reactant in such an amount that it is the combined amount of the two Acid-generating reactants in the range between about 0.5 and about 5 moles and the molar ratio the amber acid-producing reaction participant to the Phosphorus-containing acid-producing reaction parts hiser sicii moved from about 0.1: 1 to about 10: 1. Others expressed,

NS"
one can use every mole of a tetrahydroxy reactant about 0.05 moles to about 3.6 moles of a succinic acid-generating reactant and about 0.05 to about 3.6 moles of a phosphorus-containing acid-generating reactant, provided that the molar ratio of the succinic acid-generating reactant is x'S and the phos ~ phorhaltigen acid generating Reak'Sionsteilnehmers within the range of about 0.1: 1 "the preferred amounts of the three Reaktionateilnehmer _s are such that one mole of Polyhydroxyreaktionsteilnehmers with about 0.5 mole to about 1 mole of a bemsiieinsäureerzeugenden: 1 up to about 10 degrees.

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Real ti one take part and about 1 to 3 moles of a phosphorus content acid generating compound is used · A specific example of the preferred invention Products is a product which is produced by the reaction of 1 hol of pentaerythritol with 1 hol of a succinic anhydride and 2 moles of a triaryl phosphite is obtained.

When a reactant is a mixture of 2 or more individual compounds, e.g. commercially available polyvalent compounds Alcohols, welohe from a mixture of 3-, 4-, 5- or higher alcohols exist, so the molecular weight be the average molecular weight estimated from the elemental analysis of the mixture. In a similar way Manner is substituted in the case of a hydrocarbon Succinic anhydride, in which the hydrocarbon subs ti tuent derived from a mixture, for example of Olefinpolytaeren, the molecular weight from the acidity or the potential acidity of the anhydride is estimated »i.e. double the equivalent weight will be which is based on the number of acids obtained by a standard method for determining the acidity of carboxylic acids or anhydrides. The molecular weight of a succinic acid can in the same way as the potential Acidity as determined by its saponification number. It should also be noted that the lower limit of about 0.5 moles for the combined amounts of the acidic reactants, moles of the

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Polyhydroxy reactants affect stoichiometry The stubborn esterification of only one of the hydroxyl groups forms the polyhydroxy reactants, whereas the upper one Limit the number of moles χ for the combined characteristics of the two acid-generating reaction participants per MoX of the polyhydroxy reaction participant with the number of χ hydroxyl groups aiob «uf the disturbance of the esterification of all hydroxyl groups d * - FolyhydroxyreeJction participates in establishing.

A preferred way of carrying out the process according to the invention includes the reaction of a polyhydroxy reaction participant with the succinic acid-producing reaction participant with the formation of a partially esterified intermediate product, and the subsequent conversion of the biscuit product with a phosphorus-containing e-acid-sucking reaction, if the process participates in the same way the first stage, ie the formation of the partially fermented intermediate product, preferably at a temperature between about 100 and 200 ° 0 and the second stage, i.e. the reaction of the intermediate product with the phosphorus-containing reactants, can be carried out at a temperature of about 80 to about 250 ⁰ G can be performed. This particular way of carrying out the process according to the invention is preferred because it has been found that the products resulting therefrom are particularly useful for the purposes of this invention, such as in hydrocarbon oil and lubricant oil sets ο

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Another optional way of performing the method according to the invention includes a first reaction of the polyhydroxy reactant with a phosphorus-containing one acid generating reactants to form a partially esterified intermediate and a subsequent one Reaction of the intermediate product with the amino acid sucking reactant. Allowed in this regard the method further variations in the formation of the Intermediate product of a polyhydroxy substance, which with a phosphorus acid has been partially esterified * 3o, for example, the reaction of phosphoric acid with an epoxy, especially an alkylene oxide such as ethylene » oxy egg, propylene oxide, hexylene oxide or epichlorohydrin in one partially esterified glycol lead, dohc to a glycol with a free hydroxyl group and one hydroxyl group which through the esterification with phosphoric acid to a phosphoric acid «· ester group has been converted. A more specific example is the reaction of 1 hol of phosphoric acid with 3 hol Propylene oxide, which leads to the formation of the tri (hydroxypropyl) ester of phosphoric acid. This tri (hydroxypropyl) ester can then to react with a succinic acid generator Reactants used to contain the phoephorous To form esters of the present invention »

In some cases, the formation of the phosphorus-containing esters according to the process according to the invention by the Presence of a refinement catalyst in the process facilitated "

909829/1404

The known esterification catalysts are used for this purpose useful examples are titanium tetrachloride, aluminum chloride, titanium tetrafluoride, boron trifluoride, Aluminum tribromide, potassium ethylate, hatriunaethylate, calcium phenolate, sodium hydroxide, calcium oxide, benzenesulfonic acid, Toluene sulfonic acid, etc. Often a small amount such as 0.001 öew, # of the catalyst is sufficient to effect the esterification of the according to the invention to promote method. The amount of catalyst can be up to about 1% by weight of the process mixture move·

If a succinic acid ester or an ester of a phosphoric acid is reacted with a polyhydroxy reaction participant, the reaction is a transesterification, ie the replacement of the ester radical which was originally present in the succinic acid ester reaction participant or in the phosphoric acid ester reaction participant, by an ester radical which is derived from the polyhydroxy reaction participant. For example, if a dimethyl ester of succinic acid is used to react with a partially esterified glycerol, the latter by the reaction of glycerol with

Phosphorus pentoxide is formed, the product according to the invention is formed by transesterification, one or both of which Methyl radicals of the succinic reactant are replaced by radicals, which are derived from the partially esterified Olycerin ^ Derive intermediate product and methanol occurs as a by-product

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on · When triphenylphenyl phosphite reacts with a partially etherified glycerol is used, the latter being formed by the conversion of glycerol and a polyisobutene-substituted succinic acid, the product according to the invention is produced by transesterification, with one or several phenyl radicals of the triphenylphosphite are replaced by hetero radicals, which differ from the partially petrified Derive glycerine intermediate product and phenol is formed as a by-product. The latter can take part in transesterification reactions involved leg, which includes, for example, the one illustrated below, where R * is essentially a hydrocarbon radical:

^V 0 + 2HO-OH ₂ -CH (OH) -Ch ₂ OH -fr /

R 'is -CH-CO-CH ₂ -CH (OH) -CH ₂ OH j

CE ₂ -CO-CH ₂ -CH (OH) -Ch ₂ OH

CH-SO-CH ₂ -CH (OH) -Ch ₂ OH CH ₂ -OO-CH ₂ -CH (OH) -CH ₂ Oh

0 R "-CH-C * -O-OH ₉ --CH (OH) -CH" -OP (OC ^ H _1. )

CH ₂ -CO CH ₂ -CH (OH) -CH ₂ 0-P (OC ₆ H ₅ ) ₂ 0

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. - 27 -

The above contain phosphorus »!! Seter can further teilver-βstertee glycerol react does more complex products as zn form polymeric substances. The use of a succinic acid halide (such as the dichloride of a polyisobutene-substituted succinic acid) or a phosphoric acid halide (such as phosphorus pentoxide or phr iorotriochloride) with a partially esterified polyhydroxyavria leads in a similar manner. A product, sum also the halogen radical of the reaction of the recipient against an eater radical, which is derived from the partially inhaled polyhydroxy wash product. For example, the reaction of a succinic acid dichloride with ethylene glycol and phosphorus pentoxide can go as follows;

4 HO-C ₂ H ₄ -OH + P ₂ O ₅ -> 2 (HO-C ₂ H ₄ -O-) ₂ P (O) (OH) + H _{2 O}

R »-CH-CMJl
j
CH ₉ -C-Cl

R ^f -CH-COC ₂ H ₄ ~ 0-P (0) (OH) (OC ₂ H ₄ OH)

CH ₂ -COC ₂ H ₄ -O "^ 0) (OH) (OC ₂ H ₄ OH) 0

The following examples illustrate the process according to the invention Procedure·

example 1 Ss a partially brewed pentaerythritol tea is produced! by doing

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156 ropes (based on weight, 1 molar amount) of pentaerythritol from a mixture of 1130 ropes (1 molar amount) polyieobutenaubatituiertee succinic anhydride with an acid sab.1 of 99 (prepared by heating an chlorinated polyisobutenes with a molecular weight of and one chlorine content adds 4.4 # washed with 20 ^ molar excess of maleic anhydride at 205 ⁰ C) and 830 cables of a mineral oil and the resulting mixture heated for 5 hours at 15O ⁰ C and 5 hours at 200 to 21O ⁰ C and the product filtered «The by-product (water) is distilled off during heating. Bus Filtrat is a 40 # oil solution of the partially esterified ester intermediate. 310 parts (0.5 molar amount of pentaerythritol used) of sipiienyl phosphite are added to 1020 cords of this filtrate. Bas mixture is heated iO hours at 180 to 19O ° C and then at 180 ° 0 / 20mm, wherein abdeetillieren as a byproduct of transesterification ropes 96 phenol. The piltrate is a 33 # liquid solution of the phosphorus-containing ester with a phosphorus content of 2

Example 2

A polyisobutene-substituted succinic acid is prepared by heating sharkic anhydride with a chlorinated polyisobutene with a molecular weight of 1500 and a chlorine content of 4.4 $ at 20O ⁰ C to form the polyisobutene-substituted succinic anhydride with an acid number of 96, and mixing with a mineral oil the anhydride

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with Waaser at 90 tie 11O ⁰ C hydrolyzed. Ee is prepared a partially esterified propylene glycol, by reacting at 80 bie 110 ⁰ C to the above succinic acid dropwise propylene 'oxide (0.5 mole succinic acid per mole of propylene oxide) adds "the resulting mixture to 100 ° C / 7mm heated * to the residue mix an additional amount of mineral oil to make a 50 # oil solution, and then filter the oil solution. A mixture of 1733 parts of the above oil solution teilver dee "esterten Propylenglyeols and 91 ieilen Triphenylphaephit is heated for 7.5 hours at 150 to 160 ⁰ C, whereby 57 parts of phenol abdestillieren.Der Eückatarvd is diluted to form a 50 # oil solution with mineral oil and filtered. The Illtrat iat an oil solution of a phosphorus-containing ester with a phosphorus content of 0

Example ?

Bie oil solution (1890 parts) of the partially esterified propylene glycols of Example 2 and Phosphorpent0x5d (46 parts) are mixed at 23 ⁰ C. The mixture is heated for 7 1/2 hours at 50 to 60 ⁰ C and then heated to 6O ° C / 5mm. The mixture is filtered. The PIL is an oil solution of a phosphorus-containing ester

Example 4

A mixture of 670 parts of pentaerythritol and 2670 spouts of polyiaobutene-substituted amber, ureanlihydride of Example 1 (0.5 mol. Per mol of pentaerythritol) in 2194 parts

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- 50 -

Mineral oil is heated ISS 3 hours at 190 ⁰ C and then for 8 hours at 190 to 200 ° C. Nitrogen is blown through the Ssmiseb for 0.5 hours and it is filtered. The filtrate is a 4-hole oil solution of an expensive esterified pentaerythritol. To 2935! Sight of the above solution and 1060 parts of mineral oil are employed 284 · feile Piiosphorpentoxyd (0 * 8 molar quantities per molar quantity dee Pentaerytitrite used) added * The resulting mixture is heated for 5 hours at $ 11 to 120 ⁰ G, and filtered That Filtrate is a 25 # oil solution of a phoophore-containing Bster with a Hiaepüor content of $ 1.2 «

Example %

At 50 ⁰ C is a Geadeen Auss Itiiylenglycol 1 mole, 0.5 mole of phosphorus pentoxide and 0.5 Get a polyisobutene with a molecular weight of 60,000 substituted succinic anhydride "(Süurezahl 10Ö _t vtm prepared by Umeeuzung maleic anhydride with a chlorinated Polyiaobutan elnea molecular weight of 60, 000 and a chlorine content of $ 4.3 at 205 ⁰ O) in three times the volume of a mineral oil and then heated ^{at 120 to 14O 0 G for 10 hours.}

Example 6

A partially esterified octylene glycol is produced by 1 mole of octylene glycol with 0 »5 moles of one with polypropene with a molecular weight of 1500 substituted succinic anhydride with a saw rate of »OC at 200 Ms 220 ° C implements “The product --drd with ei 1 ^ n identical:>! wcht an

9 0 3 8 2 9. / 1 4 0 4

- 31 -

Dodecane and phosphoric acid (1 hol per hol ootylene glycol used) mixed. Bas calibration resulting Gemisoh is heated for 6 hours at 10O ⁰ C, water being distilled off as the esterification product lifting. The back tand is a solution of a phosphorus-containing prayers.

Example 7

Steinsäureanhydrids heating a mixture of 1 mole of the polyiaobutensubstituierten Ben * of Example 1 and 1 Hol glycerol in a two-fold volume of the mixture Toluoljwird at reflux temperature (110 ⁰ C), "wherein water is removed by azeotropic distillation. 0 _{t of} 5 ha of phosphorus pentasulphide are added to the residue ^{and the mixture is heated at 90 to 110 °} C. for 4 hours. Then toluene is removed by vacuum distillation. The residue is a phosphorus-containing ester.

Example 8

A partially esterified propylene glycol is produced by reacting 1 mole of phosphoric acid or 3.3% propylene oxide, with the by-product (water) being distilled off. 200 g of toluene and 14-95 g of the polyisobutene-substituted succinic anhydride from Example 1 are added to 390 g of these partially esterified propylene glycols. The mixture is heated for 8 hours at 158 to 163 ⁰ C * and then at 160 ° G / 1-2mm. The residue is mixed with 1200 g of mineral oil and heated to distill off toluene. The residue is filtered. The filtrate is an oil solution of a phosphorus-containing ester with a

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Phoophore content of £ 7.7 example

Be is produced a partially esterified sorbitol "by erhitat 1 mole of sorbitol and 1 mole of phosphorus pentoxide at 110 to 15O ⁰ C. The intermediate product is dissolved in colorless paraffin oil and mixed with 2.5% of the polyisobutene-substituted amberateic anhydride from Example 1. The resulting mixture is ^{heated at 200 °} C. for 7 hours and filtered.

example 10

Bs is made substituted with Olefinpolymerem succinic anhydride by reacting 1 _f 2 moles of maleic 'anhydride with 1 mole of a copolymer of 75 mole # propylene and 25 mol $ ethylene having an average molecular weight of 10 000 at 200 heated to 220 ⁰ C to a solution of the above anhydride in the same weight mineral oil ^ one adds phosphorous acid at 25 ⁰ C '2 moles Keopentylglyeol and 1 mol. The mixture is 2 hours at 12O ⁰ C and then. Heated for 5 hours at up to 180 ^° C., with water through. _{Distillation is removed o} The residue is filtered o Bas JPiltrat is an oil solution of a phosphorus-containing ester _o

Example 11 . . ·.

Following the procedure of Example 10, a containing ester is prepared from a reaction mixture of

909829/1406 ^BAD original

0.1 mol of a succinic anhydride »which with a Ieobutene-styrene copolymers (isobutene: styrene by weight 95: 5, average molecular weight 2000) is substituted, 1 hol of di (ethylene glycol) and 0.5 mol of phosphorus oxychloride

Example 12

Following the procedure of Example 10, a phosphorus-tiger ester is obtained from a Reaictionsgemleoh of 0.5 mol of the polyisobutene-substituted succinic anhydride from Example 1, 1 mol of tri (ethylene glycol) and 0.1 mol Methyl phosphite.

Example 13

Following the procedure of Example 10, a phosphorus-containing ester is prepared from a Reatetionagemiach of 1 mole of the polyobutene-substituted succinic anhydride of Example 1, 0.5 mole of triethyl phosphite and 1 mole of one Copolymers of 5 moles of allyl alcohol and 1 mole of styrene with a molecular weight of 1100.

Example 14

A phosphorus-containing setter is produced by heating a mixture of the partially esterified pentaerythritol (40 # 01 solution) and diphenyldithiophoephoric acid chloride (2 moles per mole of pentaerythritol) at 150 to 180 ^° C »

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-34.- .. "" "'· ■■■ ■ ·"

Example 1?

A phosphorous eater is produced by first heating at 120 to 20O ⁰ C 1 hol of the polyisobutene-substituted succinic anhydride from Example 1 and 1 mol of mannitol monooleate to form a partially esterified Manriitz wax product and then heating the intermediate product at 200 ⁰ C with 3 K di di (heptylpheny ^ phosphorus chloride (ie (CyH ₁ CC ₆ H ₄ O) ₂ PCl) heated in an equal volume of mineral oil.

Example 16

A phosphorus ester is produced by first heating 1 mol of the polyiaobutene-substituted: Bernateinsaureaiitiydrids from Example 1 and 1 mol of glycerol in 1000 g of mineral oil ^{at 100 to 180 0 C and then at 150 to 200 0} C the above reaction mixture with 0.5 mol of the anhydride of diethylphosphoric acid (ie (O ₂ H ₅ O) ₂ P (O) -OP (O) (OC ₂ H ₃ )),

Example 17

A phosphorus-containing ester is prepared by adding 1 mol of the polyisobutene-substituted succinic anhydride from Example 1 and 1 mol of sorbitol in which a hydroxyl group is esterified with oleic acid and another hydroxyl radical has been substituted by a Tatra (oxypropylan) radical * at 140 to 180 ⁰ C, mix the above Sealctionamaasö with an equal volume of mineral oil and

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- 35 -

then. Heating the üllöeung with a mole OO-di (4-methyl ~ 2-pentyl) dithiophosphorsaure at 100 to 120 ⁰ C.

Example 18

A phosphorus-containing ester is produced as follows: A partially esterified resorcinol (formed by heating 0.75 hol of the polyisobutene-substituted bernatein acid hydride from Example 1 with 1 hol of resorcinol in 1000 g of diphenyl ether as a diluent at 100 to 20O ⁰ C) and phosphorus pentoxide (0 , 1 mol; per mol of resorcinol) are heated ^{at 150 to 160 ° C. for 5 hours.}

Example 19

A phoaphor-containing ester is produced according to the Procedure of Example 18 with the exception that on a molar basis the resorcinol is replaced by 4-heptyl-1,2-dihydrox5 benzene is replaced.

Example 20

A phoaphor-containing ester is produced according to the Procedure of Example 18 with the exception that the resorcinol on a molar basis by 1,2-dihydroxynaphthalene is replaced.

The phosphorus-containing esters of the invention are for various purposes, including pesticides, softeners, rust inhibitors for metal treatment, corrosion

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~ 36 -

inhibition agents, high pressure agents, anti-slip agents and detergents count.

The main application of such products is their use all lubricant additives. According to the invention it was found that when using for this purpose the effectiveness of the products »to give a lubricant a specific property» in close relation to the size the hydrocarbon substituents in the carbon-substituted groups amernstelic acid-producing compounds » from which the phoaphoric worshipers derive. In particular, it was found that “products” in which of the substituents which essentially make up a hydrocarbon contains more than about 50 aliphatic ^ carbon atoms » particularly effective for the purposes of the present invention are.

The lubricating oils »in which the according to the invention substituted Polyamines which are useful as additives »can be synthetic, animal, vegetable or mineral Be of origin. Mineral lubricants become common because of their availability, their general excellence and their low cost preferred. For certain applications, oils containing any of the

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belong to other three groups. For example, synthetic polyester oils such as sidodecyl adipate and Si-2-ethylkoxyliebaeate are often preferred as lubricants for jet engines. Normally, the preferred liquid oils are Sohmiermittelöle in Viakositätsbereioh of about 40 Saybolt Universal seconde at 38 ⁰ C to about 2Ö0 Saybolt Universal Seconds at 99 ⁰ G.

You Consentration of the phoaphorhaltigen Seter as Additives in lubricants is usually in the range between about 0.01 and about 15 wt. #. You optimal concentrations for a particular application are in large measure of the operating mode to which the lubricant is subjected. For example, lubricants for use in gasoline engines about 0.5 to about 10j6 of the additive, whereas lubricant preparations for use in gearboxes and diesel engines may contain as much as $ 20 or even more of the additive. Lubricants for use in the oil-fuel mixture for two-stroke engines can be about 1 # to of the addition included.

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You invention also contemplates the presence of others Additions in the sonic agent revelations. To solo Additives include, for example, supplementary cleaning agents of the ash-containing type, yiekosing improvers Agents, agents reducing the stook point »antifoam agents, Huchatdruokmlttel, rust inhibitors and additional agents that inhibit oxidation and corrosion.

Examples of the cleaning agents containing oil are oil-oil-free neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids or organic phosphoric acids, which are characterized by at least one direct carbon-phosphorus bond, for example those obtained by treating an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a Phosphorizing agents such as phosphorus trichloride, phosphorus

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heptasulfide, phosphorus pentasulfide, PhoephortriChlorid and Sulfur, white phosphorus and sulfur halide, or Phosphorothiochloride are produced. JHe most common The salts of oleic acids used are the saIae of Hatriume, Potassium, Lithium, Galeturns, Magnesiums, Strontiums and Barium.

The expression "basic salt" refers to the metal salts in which the metal is present in etoobiometrically larger amounts than the organic acid radical. Methods commonly used for the preparation of the basic salts include making a mineral oil solution of a su ire with an etochiometric excess of a metal-containing neutralizing agent like metal oxide, -hydroxyd, -oarboaat, -bioarbonat or -eulfid at a temperature of about 5 "° C and filtering the resulting mass. The use of a "promoter" in neutralization to aid in the incorporation of a large excess of metal is also known. Examples of compounds useful as promoters include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; Alcohols such as methanol, 2-propanol, octyl alcohol, celloeolve, garbit oil, xethylene glycol, stearyl alcohol and cyclohexyl alcohol; Amines such as aniline, phenylenediamine, phenothiaein, phenyl-ß-naphthylamine and

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~ 40 -

Bodecylamine. One particularly effective method of making the basic salts is by mixing an acid with an excess of a basic alkaline earth metal neutralizing agent, a phenolic promoting compound, and a small amount of water and "carbonizing" the mixture at an elevated temperature such as 60 to 200 ⁰ O.

The preparation of a prayer Gente of basic sulfonate is illustrated below: A Gemsich aua 490 parts (by weight) mineral oil, 110 parts of water, 61 parts of heptylphenol, 340 parts Bariummahoganyaulfonat and 227 barium oxide, it is for 0.5 hours at 100 ⁰ C and then heated to 150 0 · Then carbon dioxide is bubbled into the mixture until the mixture is essentially neutral. The mixture is filtered and it is found that the Fitrat has a sulphate ash content of $ 25.

The preparation of a basic barium salt of a phosphorus «· acid is illustrated below: A polyisobutene weight of 50,000 with a molecular is mixed for 6 hours at 200 ⁰ C with 10 percent by ¹ ^ phosphorus pentasulfide.. Bas resulting product is purified by treatment with Bampf at 160 ⁰ C hydrolyzed to give results in an acidic intermediate. The acidic intermediate product is then converted to a basic salt by adding 2 moles of barium hydroxide and 0.? Moles of phenol mixed

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oarboniaiert and dae mixture at 15O ⁰ C to form einee liquid product.

The phoaphorhultigen Seter are particularly intended for use in combination with high pressure "and korrosionshemsenden Zusätzenwie Metalldithiooarbanaten, xanthates, the Dithl © phosphates of Group II metals and their Epoxydaddukte, hindered phenols, sulfurized Cyoloalkanen, Dialkylpolyeulfiden, sulfurized fatty esters, phoaphorgesohwefelten fatty esters" Erdalkalisalaen ulkylierter phenols »DIalkylphosphites Iriarylphosphiten and Katern der Dithiophoaphorsäuren. Combinations of the phosphorus-containing · !! Esters of the above-mentioned formulas are particularly desirable for use in lubricants which must have outstanding extreme pressure and oxidation-inhibiting properties.

The group II metal dithiophosphates are the salts of acids of the formula:

H ₁

H ₂

in which R ₁ and Hg are essentially hydrocarbon radicals ο examples of metals for forming such salts

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Barium, calcium, strontium, zinc and cadmium. The barium and zinc dithiophosphates are particularly preferred «The essentially hydrocarbon-forming radicals in the dithiophosphoric acid are preferably alkyl radicals low or medium molecular weight and alkylphenyl radicals, i.e. those which are in the alkyl group from about 1 to have about 30 carbon atoms. Illustrative alkyl radicals include: ethyl, methyl, laopropyl, isobutyl, η-butyl, sec. »butyl, the various amyl alcohols, n-Hexyl-methylisobutyl-oarbinyl, heptyl, 2-ethylhexyl, diisobutyl, Isooctyl, nonyl, behenyl, decyl, etc. Illustrative lower alkylphenyl radicals are: butylphenyl, Amylphenyl, di-amylphenyl, octylphenyl, etc. cycloalkyl radicals Bind can also be used and these are the main ones Cyclohexyl and the lower alkyl cyclohexyl radicals. Other essentially hydrocarbon radicals are also useful, such as tetradeoyl, Octadecyl, Sicosyl, Butylnaphthyl, Hexylnaphthyl, Octylnaphthyl, cyclohexylphenyl, naphthenyl, etc. Many substituted hydrocarbon radicals are also useful, for example chloropentyl, dichlorophenyl and dichlorodecyl.

How to get to the dithiophosphoric acids, from which the salts of the Group II metals of the invention are known to those skilled in the art. You are won by * the reaction of phosphorus pentasulfide with a Alcohol or phenol., Sa become 4 moles of alcohol or phenol

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per mole of phosphorus pentasulfide reacted, the Uiaeeteung can be carried out within the temperature range τοη about 50 to about 200 ⁰ O. The production of QO-di-n-hexyldithiophosphoric acid consists in the uresis τοη phosphorus pentasulfide with 4 moles of n-hexyl alcohol at about 100 ⁰ C, the training takes about 2 hours. Ss becomes U waseeretoff released and the residue is the defined Acid. The manufacture of zinc or barrels of this Acid can be produced by reaction with zinc oxide or barium oxide. B's is simply mixing and heating the two Reaction participant sufficient for the reaction to take place and the calibrating product is for the purposes of the present invention is sufficiently pure.

Particularly useful dithio phosphates of the group metal II can be prepared from dithiophoreous acids, w. * Ei this in turn by the reaction τοη Phosphorpsntasulfld Bit ßeeiachen the alcohols are obtained. The usage Such Oeadsche enables the use of cheaper alcohols which themselves are not oil-soluble dithiophosphoric acids result. A mixture of prophylaxis and hexyl alcohols can be used to create a very effective oil solution Suck metal thiophosphate. For the same reason mixtures of simple dithiophoreous acids (i.e. acids, what were made from iron alcohol) with zinc oxide

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or Bariunoxyd be umgesetst "öllöallene by less costly" Sals "au erseugen"

Another class of Thiophosphatausütee that "for use are provided in the Ungen erfindungegemässen Sohmiennittelaubereit- include the adducts of Hetalldithlophosphate described above with an epoxy. The metal dithiophosphates which can be used for the preparation of such adducts are mostly zinc dithiophosphates. The epoxides can be alkylene oxides or arylalkylene oxides, examples of the arylalkylene oxides are styrene oxide, p-ethyl styrene oxide, X-methyl styrene oxide, 3-β-naphthyl ~ 1-5-butyleneoxy, m-itodecyl styrene oxide, and p-chlorostyrene oxide. The alkylene oxides mainly include the lower alkylene oxides in which the alkylene radical contains 6 or fewer carbon atoms. Examples of such lower alkylene oxides are ethylene oxide, propylene oxide, 1,2-f Butenoxyd _t Triraethylenoxyd, Tetramethylenoxyd, Butadienmonoepoxyd, 1.2 ~ Hexenoxyd and Propylenepichlorhydrin. Other epoxies which can be used here include, for example, butyl-9-10-epoxystearate, epoxidized soybean oil, epoxidized tung oil and epoxidized copolymers including styrene with butadiene.

The adduct can be obtained by simply mixing the dithiophosphate and the epoxy. The reaction is usually exothermic and may 1st Within Welter temperature · - limits from about ⁰ ° C to et v / a 200 ⁰ C are performed.

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Since the reaction is exothermic, it is best carried out by passing one reactant, usually the epoxy, in small proportions to the other reactant added for convenient control of the reaction temperature au achieve. Me reaction can take place in a solvent such as benzene, mineral oil, naphtha, or n-hexane are listed.

The chemical structure of the adduct is unknown. More than a mole, sometimes as much as 4 moles of the epoxyda can can be combined with the pithio phosphate to be useful Forming products. However, it has been found that adducts, which by the reaction of one mole of the Dithiophoaphata with about 0.25 mole to about 1 mole of a lower alkylene oxide, in particular ethylene oxide and propylene oxide are obtained, are particularly useful and are therefore preferred.

The soaking agent formulations can contain metal detergent additives in amounts which are usually in the range of about 0.1 to about 20 wt. #. In some applications, such as marine diesel engine lubrication, the lubricant compositions may contain as much as 30% of a metal detergent additive. They can contain other additives such as extreme pressure additives, viscosity index improving agents and agents reducing the pour point, each in amounts which are within the range from about 0.1ji to about 10 * 5 _Λ

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The following examples illustrate the clothing old clothes of the present invention, all of which Prosent information on the weight:

Example I. 3AB 20 Mlneralsehmieröl with a content of 0.5 # dee product Clay example Example JI

MineralsohmierBl SAB 30 with a content of O, 755 & des Product of Example 2 and 0.156 phosphorus as barium salt of di-n ~ nonyldi thiophosphoric acid.

Example III

MineralBohoieröl SAl 10W-30 containing O, 4 $ dee product of Examples

Example IV

Mineralechmierul SAS 90 containing 0.1 # of the product of Example 4 and 0.155t of the zinc salt of an equimolar Mixtures of di ~ cyolohexyl ~ dithlopho-phosphoric acid and di-iaobutyl-dithiophoephoric acid.

Example Y

Mineral simmering oil SAS 30 with a content of 2 # of the product ▼ on example 4 «

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Example VI Mineral chai oil SAB 20W-30 with a content of 5t> des Products from example 5 Example YII Mineral lubricating oil SAS 10W-30 with a content of 1.5 * d < Product of Example 2 and 0.059 »phosphorus as zinc alf

a ditniophosphoric acid, which by Uasetaung von

Phosphorus pentasulfide with a mixture of 60 ^ (mol)

p-Butylphenol and 4O? 6 (Hol) n-Pentgrl alcohol produced let

Example YIII

Hineralaohmieröl SAS 50 with. a content of 3 # of the product of Example 4 and Ο, ΐίό phosphorus as Caloiumealz dee Dihexjridi thiopbosphats.

Example IX Mineral lubricating oil SAB 1OW-30 with a content of 2yi des Product of Example 2 _f O, O6? 6 phosphorus as 2inlcdi-n-

ootyldithiophosphate and V & sulfataaohe as barium mahogany sulfonate »

Example X

Mineral lubricating oil SAE! K) with a content of 5% of the "product" on Example 10, 0.1 £ phosphorus ale zinc as a mixture of equimolar amounts of ui-isopropyldithiophosphoric acid and di-n-decyldlthiophoapioreic acid, and 2.5 # sulfate ash as

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- 4β -

basic Bariuiadetergent prepared duroh carbonizing at 15O ⁰ C a mixture consisting of mineral oil, and 1.5 mol Bariumdidodecylbenzolaulfonat barium hydroxide, In the presence of a small amount of water and 0.7 mol of octylphenol as a promoter "

Example XI

Mineral lubricating oil SAE 10W-30 with a content of 6 $ of the product of Example 17, 0.075 $ phosphorus as zinc-n-octyldithiophosphate, and 5 $ of the barium salt of an acidic mass "which is obtained by reacting 1000 parts of a polyisobutenes with a molecular weight of 60,000 with 100 ropes of Phoeptaorpentasulfid at 200 ⁰ O and hydrolyzing the product with steam at 150 ⁰ C was produced.

Example XII

MineralschmieröX SAB 10 with a content of 2 $ of the product of Example 20,0,075 ^ phosphorus as an adduct of zinc dicyclohexyldithlophosphate, treated with 0.3 mol of ethylene oxide, 2% sulphurized sperm oils with a sulfur content of 10 $, 3.5 ^ of a poly - (alkyl methacrylate) as a viscosity index improver, 0.02 ', J of a poly (alkyl methacrylate) as a pour point depressant, $ 0.003 of a poly (alkylalloxare) as an anti-foam agent.

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Example XIII

Mineral lubricating oil with a content of SAB 10 1.53 * of the product of Example 19, O, O? 5 £ phosphorus as an adduct obtained by Erhitsen of ZinJcdinonyldithiophoephat Bit 0.25 Koi 1 '2 ~ Ηβχβη-oatyd at 120 ⁰ C »A» sulphurized methyl Esters of tall oleic acid with a »Soap content of £ 6 of a polybutene viscosity index verbeeserere, £ 0.005 of one

Poly (alley imethacrylate) as an anti-foaming agent and 0.5 pounds of lard oil. Example XIY

Mineral lubricating oil SAB 20 with a content of 1.5% of the product of Example 2, 0.5 ^ didodecylphosphite, Ti »of a sulphurized sperm oil with a sulfur content of 9%, a basic calcium impurity, produced by carbonizing a mixture of mineral oil, calcium mahoganysulphonate and 6 Get calcium hydroxide in the presence of an equimolar mixture (10% of the mixture) of methyl alcohol and n-butyl alcohol as a promoter at reflux temperature.

Example XY

MineralschmierSl SAB 10 with a content of 25 ^ of the product from Example 13 »ο» ο79έ phosphorus as zinc diootyldithiophosphate, 2? S of a barium detergent made by neutralizing the hydrolyzing reaction product of a Polypropylene (molecular weight 2000) with 1 mol of phosphorus

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pentasulfide and 1 NOX sulfur, where a with barium hydroxide is neutralized "3 # of a barium eulfonate cleaning agent", produced by carbonizing a mineral oil solution of mahogany acid and a 500 # Lgen stoichiometric excess of barium hydroxide in the presence of phenol as a promoter at 180 _{° 1} 3 # of a complementary asoheloaen detergent Produced by copolymerizing a mixture of 95% by weight of deoylraethacrylate and 5% by weight of diethylaninoethyl acrylate.

Example IYI

Mineral ohmler oil SA £ 30 ct with a content of 2 / * of the product of Example 20, 0.1 # phosphorus as zinc di "n ~ hexyldithiophosphate" 1O ^ elnee chlorinated paraffin wax with a chlorine content of 4 (¥, 2 $ dibutyl tetra sulfide, 2 * 4 sulphurized bipentens, 0 ₉ & t oleyleaid, 0.003 '* of an anti-sustaining agent, 0 »O2 ^ of a part which lowers the pour point and 3 ^ of a viscosity index verbeaeerere ·

Example XYII

Mineral ohmic oil SAB 10 with a content of 3 ^c a of the product of Example 5, 0.075 ^ phosphorus as the zinc salt of a dithiophosphoric acid, produced by the reaction of phosphorus pentasulfide with an equimolar mixture of n-butyl alcohol and bodecylaDcohol, 3i> a Bariiimreinigungsiaittele, produced by Carbonizing a Hineral Oil Solutioni

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which contains a mole of spere oil, O ₉ 6 hol octylphenol, 2 hol barium oxide and a small kens water, at 150 ⁰ C.

Example XYIII Mineral cooking oil SAB 20, containing 2} C of the product of Example 12 and Q, 07j * Phosphorus «la Ziiucdi-n-octyldithic

phosphate.

Example XIX

Mineral oil 8AE 30 with a content of yf> of the product * of Examples H and O, 1 £ phosphorus as zinc di (ieobutylphenyl) dithiophoephate.

Beiapiel JDC Hirieralacbmieröl SAS 50 old a content of 2t des

ron example 9 «

Example IDCI

nineralachBleröl SA35 90 alt a «content of 35 * of the product of Example 11 and 0.2 ^ phosphorus as a reaction product of 4 NoI turpentine with 1 mol of phosphorus pentasulphide «

Example XXII

Mineralactuoieröl SAB 90 has a content of yf> of the product of Example 12 and 0.2 * 4.4'-Kethylen-bie ~ (2o6-di-tert-butylphenol).

ORIGINAL BATHROOM 909829 / H04

Example XXIII

Mineral lubrication oil SAB 30 with a share of 2 years of the product ▼ on Example 13 and 0.1 £ phosphorus as Phenyläthyi-di-cyclohexyldithiophoephat.

Example XXIT

Mineral lubricating oil SAS 90 containing £ 5 of the product of Examples 1 and 14 of the calcium salsa of the sulphurized "Phenol" obtained by the reaction of 2 moles of heptylphenol and 1 haul of sulfur.

The lubricants given above are merely illustrative embodiments. The scope of the invention includes the use of all of the additives illustrated above as well as other additives in the broad web of US Pat

invention described here.

The usefulness of the phosphorus-containing esters according to the invention as additives in soaking agent preparations is illustrated by the results of an oxidation and cleaning test, using a 350 cm ⁵ sample of the lubricant, which contains 0.001% by weight of bubble naphthenate and 1.5% by weight of the chemical-free additive contains, placed in a 5.1 χ 38, lon (2 χ 1finches) borosilicate tube. A 34,925 x U9,225mn (1 3 / 8x5 7/3 inches) steel plate SAB 1020 is immersed in the testul. The sample is then used for

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heated for a set period of time at 149 C while bubbling air through them at a rate of 10 liters per hour. The oxidized sample is cooled to 49 ° 0, homogenized with 0.55 # water, left to stand for 24 8 hours at room temperature and then filtered through two layers of Whataan pilgrim paper at 20 m Hg. The weight of the washed with naphtha and dried lriederschlag is taken as the Mad for the effectiveness of the additive, inhibit the oxidation su and disperse the sludge formed during the test IU. The greater the weight of the precipitate *, the less effective the additive will be. The results of the tea are shown in Table I below. Bas is used in the test of the lubricant Srundöl a conventional refined Hid-Continent-Mineralul having a viscosity of about 200 Saybolt Universal Seconds at 38 ⁰ C.

Table I.

Invention days 1 2 test Test results «
mg slurry per 100cm ^J essential product 3 Hours. lubricant • 3 250-400 none 48 800-1200 none 96 > 1600 none 144 3.9 Product of example 144 7.9 Product of Ex. 144 2 product of ex. 96 7th Product of example 144

The effectiveness of the substituted polyamines as detergents * Uses in lubricants for diesel engines, which under relatively severe working conditions »is demonstrated by the results (Table II) of the CRC ~ L-1 Haeohinentest8,

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BATH ORIGINAL

»54 ~

which is also known as the Caterpillar IE Seat. For this test, the lubricant composition of the crankcase of a four-stroke diesel engine is used, which has a compression ratio of 15: 1 and is driven for 120 hours under the following conditions: speed 100 rev / mlnj BTD input per hour 2900 to 3000; Load 20 horsepower; Temperature of the water jacket 79 to 82 ⁰ C; oil temperature 60 to 66 ⁰ C. A diesel fuel is used, which has a sulfur content of either 1 # or 0> 4 £. The lubricant is evaluated based on vegetable (1) piston cleanliness (rating scale of 100, with 100 indicating no deposit and 0 indicating heavy deposits) and (2) Extent of the Elngan filling.

Table II Oeteetetes Hingen- Rating of the Schnlermelttel filling 1> Piston sophistication

\ β. Hineralsohmlerul SAE 30 old with a content of 1.68 pounds of the product of Example 1 - \ i » 97.0

- Pateat response -

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Claims (1)

Claims 1.) Process for the production of phosphorus-containing esters, ge « characterized by the reaction of a polyhydroxy compound of the formula: in which R is a hydrocarbon radical and ζ is a whole number greater than 1, with about 0.5 to χ mol of an acid-forming mixture (A) of a succinic acid-forming compound from the class of carbon-substituted beroetic acids and their halides, beers and Anhydrides with at least about 50 aliphatic carbon atoms are hydrocarbyl substituents, and (B) a phosphorus-containing acid-forming compound from the class of phosphoric acids, phosphorous acids and their halides, ethers and anhydrides, the molar ratio of the aminic acid-forming compounds to the phosphoric acid-forming compound The range ron is about 0.1i1 to 10 »1. 2.) Process for the production of phosphorus-containing Beter, marked by the reaction of 1 mole of a polyvalent one Alcohol with up to about 8 hydroxy radicals, with about 0.5 to 8 KoI of an acid-forming mixture from (A) one olefin polymer-substituted succinic anhydride, in which 909829 / U04 Si the Olefiapolyoereubetituent βία molecular weight ron about 790-5000 spreads, and (B) a "frlkohlenwaseeretoffphosphit old to m about 50 carbon atoms in each coals ~ waaecretoftradlkal, wherein the molar Yerhältnis dts Bernstein * eäiuceanhydridB sum Ehosphlt Within the range yon about 0.1: 1 to 1OtI. * 3 ·) The procedure according to claim 2, furthermore known by the fact that the polyhydric alcohol 3 to 6 HjdroxyradUcale auTweiat » 4.) Terfehren naoh Anepraoh 2, further characterized in that the Trikohlenwaeeeretoffphoaphit Triphanylphoepiiit let · 5.) retracts, but the preparation phoephorhaltiger Eater, ge-) kennseichnet by the reaction at a fenperatur above about 100 ° 0 τοη 1 mol of a polyhydric alcohols with about 3 to 6 hydroxy radicals having about 0.5 to 3 mol of a eftureblldenden mixture of (A ) a polyisobutene-substituted succinic anhydride in which the polyisobutene substituent has a molecular weight of about 750 to 5000, and (B) a triaryl phosphite, the molar ratio of the succinic anhydride sram Fhosphlt being within the range of about 0.1: 1 to 10t 1. 90 9-8 29/1404 6.) The method according to claim I ₉ furthermore characterized by the fact that the polyhydroxy compound is in poly (oxyalkylene) glycol. 7 ·) Process for production containing phosphorus? Sater> characterized by the fact that »an intermediate product which is partially breathed is formed by the reaction at a temperature above * half about 100 0 of a polyhydroxy compound of the formula: ^ in which R is a carbon radical and χ is a whole number greater than 1, with a amber acid-forming compound from the group of carbon-substituted succinic acids and their halides, batteries and anhydrides Bit At least about 50 aliphatic carbon atoms in the carbon dioxide atom at a temperature of about 10 o, and above about 10 o ⁰ C converts this intermediate product Alt of a phosphorus-containing, acid-forming compound from the class Fhoanhora acids, phosphorus acids and their halides, esters and anhydrides, the amount of succinic acid-forming compound and phosphorus-containing acid-forming compound being about 0.5 to χ mol xy per compound of polyhydrides, and the molar ratio of the amernate acid generating compound to the phosphorus acid generating compound is within the range of about 0.1-1 to 10: 1. 909829 / UOA β.) Method * ur production of phosphorus-containing setter, characterized in that nan forms a partially esterified ester through conversion at a temperature τοη above about 10O ⁰ O of a polyhydric alcohol with about 3 to 6 hydroxy radicals with an olefin polymer-substituted amberateic anhydride, in which the olefin polymer substituent has a molecular weight of about 750 to 3000, and that the ^{intermediate product is reacted with a sriaryl phosphite at a temperature above about 10O 0} C, the total amounts of succinic anhydride and fhoephite being about 0.5 to 3 hol per hol of polyhydric alcohols and the molar ratio of succinic acid hydride to phosphate is within the range from about 0.1: 1 to 10 »1. 9 ·) Method according to Anepruoa 8 _t further characterized in that the polyhydric alcohol has 4 hydroxy radicals · 10.) The method according to claim 8, further characterized in that the olefin polymer-substituted succinic acid ~ anhydride is a polyobutene-substituted succinic anhydride. 11.) The method according to claim 8, further characterized in that the friarylphophite is sriphenylphophite. 9 0 9 8 2 9/1404 12.) A process for the production of phoophore-containing beers, characterized in that "μ" ma "in partially rereeterte" Zwieoheaprodukt "forms by the reaction at a temperature above about 100 ⁰ % of a tetravalent alcohol" it about 4 bl "12 Carbon atoms "with about 0.5 to 1.5 Hol a polyieobutene-substituted succinic anhydride", in *. ,, the polyobutene substituent has a molecular weight of about 750 to $ 000, and that the "swiachenprodiUr at a temperature above about 100 ⁰ " it about 0.1 bi · 1 mol tinea Triarylphoephite mattst. 13 ·)? Learn aaeh Aneproeh 12, continue daduroh eeichnet that the tetravalent alcohol pentaerythritol did 14.) Method according to Anapruch 12, further thereby gekenr jwlohnet, daaa da «Triarylphoephit Triphenylphoephit let. 19 ·) Product of the procedure after Anaprueh 1 « 16.) Product of the method according to claim 14 17 «) SohmieraitteläBakereitune, characterized in that daaa ■ ie from a »predominant part of a SohvisrOla and a« subordinate fail dta products »dta process according to Anapruch 1 beeteht, bew. Data it contains these parts « BAD ORIGINAL 909829 / .UOA 18.) 8ohBlerBdttelsubereitung ₉ because it consists of a predominant part of a Sobs! * Rule and a subordinate part of the products * the process according to claim 14, because it contains these bed parts. "19 ·) Switchboard preparation, daduroh kermselohnet, daea ale aas a «predominant fur of a lubricating oil, a subordinate part of the product of the method according to example 1 "and a" subordinate part of a Dithiopboephats of a group II metal, bsw that it contains these components » BATH ORIGINAL 909829/1404