DE2252076A1 - BENZENE DERIVATIVES SUITABLE AS ADDITIVES FOR LUBRICATING OILS, PROCESS FOR THEIR PRODUCTION, AND LUBRICATING OIL MIXTURES CONTAINING THESE - Google Patents

Description

2252Q76

LAWYERS

DR. JlJR. DIPL-CHEM. WALTER BEIL

ALFRiO HOiPrENER

DR. JUR. DIPt ₁ -CM ¹ EM. H.-J. VVOLFP 2.?, Okf. 1972

DL JUR. HmHS CMIi. AX

FRANKFURT AM MAIN-HOCHSI

AUELONSTRASSE58

Our No. 18 210

Chevron Research Company San Francisco, CaI., V.St.A.

Benzene derivatives suitable as additives for lubricating oils, processes for their production and those containing them Lubricating oil mixtures.

The invention relates to benzene derivatives useful as additives for lubricating oils and also relates on intermediate products for these compounds, processes for the production of these compounds and lubricating oil mixtures, which contain these compounds. Lubricating oils are extremely

309820 / IOt> 2

Used numerous occasions «Under most conditions of use the oil comes into contact with air, often at high temperatures and in the presence of metals or chemicals Compounds that act as oxidation catalysts »Lubricating oils, whether natural or synthetic, are subject to these .conditions of a series of oxidation reactions The harmful consequences of such oxidations are an increase in viscosity, the formation of carbonaceous substances and the formation of various oxygen-containing impurities, as noted the impurities contain lactones, ketones, aldehydes, esters, alcohols, hydroxy acids and anhydrides and peroxides, »The acidic and peroxidic impurities attack metals, cause bearing corrosion and accelerate Rust and wear processes. Acidic contaminants are also a major source of oil-insoluble products that cause seizure the piston rings and lead to sludge separation and the 01 flow Bwhinder »Aiitioxidanticn are added to the lubricating oils, to delay oxidation of the oil »

If the pressure or speed is between relative the oil film that normally is present between the fii jhen, squeezed or ab, '; erieb:; ii. When this happens, there is no full lubrication more and it comes to partial or ureiizschniierung · in the Iron lubrication is a significant part of lubrication Flee metal-to-metal contact. This contact often leads to an extraordinary misery or even to damage the surfaces moving towards one another pasture added to the scrub munchies

BATH ORIGINAL

309820/105?

to support the lubrication of the moving metal surfaces under the conditions of boundary lubrication.

In US-PS 2,265,582 trialkylated monohydroxyphenols, those in the ortho positions to the hydroxyl group have at least one alkyl group which contains three or more carbon atoms, described .. This hindered Phenols designated are supposed to prevent oxidative changes in the oil hydrocarbons when they are in mixed in small amounts.

High-pressure lubricants are known from US Pat. No. 2,073 which contain esters and anhydrides of organic thioacids. Useful mixtures contain S-ethyl thiobenzoate and benzyl thiobenzoate.

Reports vol. 95 * p. 2861 (1962) describe the reaction of active methylene compounds such as cyanoacetamide with carbon disulfide, which is followed by the reaction with various halides, in which various dithio derivatives are formed.

Finally, in US Pat. No. 3,609,081 there are organic mixtures as described in lubricating and heating oils containing secondary trialkylphenoies in which the secondary alkyl groups Have 6 to 9 carbon atoms * The phenols are described as antioxidants for organic mixtures.

The compounds of the invention include esters of 4-Hydroxy- and ^ -thiol-dithiobenzoesätiren, 1,4-Mhydro-1-oxo-ö »

dit. iomethylontoenzole and 1, Jf-dihydro-l-oxo -'- l- (l, 3-dithincyclopent - ^ - ylideii) ijüiii'iOle, the n;: i nucleus alkyl substituents in wear both ortho-Stellmi .cn to the hydroxy, Tliiol and Oxotfrupr> e, which hinder these disruptions steric.

These compounds are used as additives for lubricant loops £ jeei, 'jnet. The essential nature of this additive © protects the oil from oxidation and is used in many FHs. 11 on ausscrdom the Α ± (·; οη- properties of a jiochdruckr.olviiei-niitic Ls «

According to (linora only on ] orlan 1 dar ΰι-ΓΙΐΐ ^ ιιηβ vcrden Es tor von / | - .'7-droxy- and 4-thio] -ditJiiol) enzoic acids,!, ^ - Dihj'djro-l-oxo ^ ) -ditJiioniothylenbenzoIe and 1 '(-Dilij'dro-l-oxo-'l- (l, 3-ditliiaoyrlopent-2-ylidene) bonzole bitter "tnl.lt which the Alk Fora ^- .'l" ^xib: t..f.tiujnten nri in both O-otollunrieu for hydroxy, "fliiol- and O;: ^o;; r ii))] he wear the -5 (£ (τΐ · ηιρροη ^steri. ch hinder.

J) ie erf indun £; sfiem issen esters and substituted benzenes leiton from 4-hydroxy and 4-thiol ditliiobenzoesäuren from "Dar ilen- zoesüurerest in both ortho-Stellunc'on for hydroxyl or thio! group substituted by ilk / lsubsitiiouten which hinder the hydroxyl or thiol groups steric. Alkyl substituents with four or 'flour' carbon atoms are used, which are more often ve rz v / ei et than ßeiv.dlcotli /; are, z, ^, jt-butyl, t-Λίΐ. I and the like.

Preferred compounds g-eniüss dor .ir-findunij are esters of 4-llydroxyutide 4-T] iiol — ditJiiobenzoos; iuren, the following formulas own;

ÖAD

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Χϊ

Ri

XV

l, ^ - Dihy (lro-l-oxo-4-ditliio: aethylenbenzenes doi the following formula:

κ.

/ V _x

^ -S 5-R ₅ -

and!, il-üi

dor the following formula:

-a-ylidene) benzenes

K-

O Il

r%

«AD

C C

In the above formulas I, II, III and IV:

l) Ii_ and U ^ each alkyl ^ rup ion, which sterically hinder the adjacent hydroxyl, thiol or oxo group and contain four or more, preferably four to nine carbon atoms in a branched chain, wLe z.'iJ. jfc-butyl, J; -ainyl _# js-IIexyl, j3-Iieptyl, _s-octyl _t £ -nonyl and others;

: i) K, and R, respectively Alk lt ylf; rup> eu, from 1 to 20 carbon afcome contain WLE methyl, ^ methyl, i'ropyl, I ^ s_opro |) yl, butyl, iso butyl, sec -. Butyl, tert -i.iut_yl, I'enty.l, isjoamyl, tert -anyl, hexyl, Hopfcyl, octyl, nonyl, decyl, iodecyl, pentadecyl, icosyl and others; Hydroxyalkyl such as -ιί-ΟΗ; Te may be 2 to 5 Kohlenstoffatoiae include straight or branched chain and l ^ ie; Hydroxyallcyloxyalkyl such as _e -HOH-OH or Hydroxyalkylpoly (oxyalkyl), such as ^ ^ UO U-OII, in which the Alkyleiire designated It *. zl), ethylene, 1,2-propylene, 1,2-butylene, 1,2-Pentylcn u _o a. and η 2 to 6 ISTJ aralkyl such as benzyl _0, p-xylyl, etc., or aryl such as phenyl, 4-tolyl and others;

3) R ^ is an alkylene group containing 1 to 8 carbon atoms, like z.H. Methylene, ethylene, trimethylene, tetramethylene, Pentamethylene, hexamethylene, heptamethylene, octamethylene inter alia;

4) R “hydrogen, alkyl as defined above for It or aryl such as z, B _e phenyl, tolyl, xylyl, etc., where R _{7 is} preferably hydrogen;

5) X oxygen or sulfur and preferably oxygen and

6) Y is hydrogen or a metallic cation, which is iim that of an alkali salt such as sodium and potassium or that an alkali metal salt such as calcium and barium, where Y is preferably hydrogen.

3 0 9 820/105? BATH ORIGINAL

To explain the esters of dithiobenzoic acid according to the invention let the following connections be raigefülix-t:

I 3 9 5-Di-Jb-butyl-4-liydroxy-di tliio.benzo esäuremetlayles t er II 3 »5-Di-j; -bx: it3rl - ^ - hydroxy-ditliiobenzoic acid ethyl ester III 3» 5-Di- j ^ -but3 ^r l - ^ - liydrox3 '· -dithiobenzoic acid-n-octyl ester IV 3,5-di-j; -ainyl - ^ - hydi ^ ox3 ^r -ditliiobenzqesäm? e - n-oct3> -lester

V 3,5-Di-Jb-butyl - '<· - tliiol-dithiobenzoic acid-n-octyl ester VI 3i5-Di-ib-butyl-4-hydroxy-ditliioben3oic acid-hydroxy-propylene ester

VII 3 »5-Di-jfc-butyl-'i-liydrox3 '- di.tliiobenzo es.iur e-hydrox3rprop3'" lenox3 ^r prop3 '"l enes t er

VIII 3 1 5-Di-_t-butyl - ^ - li3 '"di ^> ox3' - ditliiobenzoes; iure-hydrox3rpron3'-leiidiox3 ^r proi) -ylenester

IX bis (3 »5 - di-t-but3-l-fy-] iydro:? ^ -.- di tliiobenzoic acid) methyl en ester
X bis (3 »5-i) ii-lrat. \ '- l - ^ - h3 ^r drox3 - (lit] iiobeiizoic acid) ätli3'lenester

XI Bis (3 »5-3) i-Ji-l3ut3 ^f l-4-liydrox3 '' - dit] iiobenzoesäu.re) triinet ^ lenester

'Ä _N G iSrläuterung the errindungsgemässen Metla - <' l (.. nbenzole Seian the .folgenden connections ongerülirt:

XII 1, ^ -Dihydro-1-oxo-n, 6-di-ib-butyl - ^ - diiaethyltliioiiiethylenbenzene

XIII 1, ^ -Dil ^ dro-l- thion- 2, o-di-jt-but ^ / l - ^ - dimetliylthiomethyl enbenzene

XIV 1,4-Dihydro-1-oxo-2 _f 6-di-jt-butyl - ^ - di-n-octylthioiiieth3'lenbenzene

XV 1,4-Dihydro-1-oxo-2 ₁ 6-di-ic-amyl-4-dih.3 ^{: r} droxypropyleneth.ioi: iethylene benzene

XVI 1 , ^ Dihydro-1-oxo-2 , 6-di-jt-butyl-4-dihydroxyproTiylentliiometliylenbenzene

309820/105? ^{& AQ}

Z _u r explanation of the ci ^ fi uluncsgemussen DitJiiacyclopentylidenbenzole the following compounds may be unfjGführt:

XVII 1,4-dihydro-1-oxo- ?, 6-di-j; -butyl-4- (1 _t 3-dithiacyclopent-2-ylidene) -benzene

XVIII!, ^ - Dihrdro-l-oxo- ^ jo-di-i-butyl- ^ Cl-methyl-l ^ -dithiiicyclopent-2-ylidene) benzene

XIX 1,4-dihydro-1-oxo-2,6-di-i-amyl-4- (1 ₁ 3-dithiacyclopent-2-ylidene) -banzole,

According to a second feature of the invention, the intermediate products used for the above dithiobenzoic acid esters and substituted benzenes are 4-thiol- and 4-hydroxy-dithiobenzoic acids which have alkyl substituents in the nucleus in both positions ortho to the hydroxy or thiol group which this hydroxy. or sterically hinder thiol group _o

Preferred intermediates according to the invention are 4-thiol and ^ -hydroxybenzoic acids of the following formula:

S SY

where X, Y, R_ and R have the meaning defined above «

According to a third aspect of the invention are methods of manufacture of the 4-thiols described above as intermediates and 4-hydroxy-dithiobenzoic acids, characterized in that about one equivalent of a phenol or thiophenol attached to the core Alkyl substituents in both ortho positions to the hydroxy or

309820/106?

BATH ORIGINAL

_ 9 -

Thiol group which sterically carries the hydroxyl or thiol group hinder, with about two equivalents of a strong proton acceptor is combined, wherein a first iieaktionsprodukt is obtained. This first product is then reacted with about one equivalent of carbon disulfide, which is the intermediate product is formed in the form of a dithiobenzoic acid radical

This acidic radical is likely to be found as the double salt of the Cations of the proton acceptor. The dithi © benzoic acid can, if desired, by acidifying the reaction mixture with at least two equivalents of a proton donor such as Jä "B" one Mineral acid can be isolated, this Bithiobensoesaure in free form. In general, however, it is more convenient to be simple the acid in the form of the radical without isolation from the reaction mixture as an "intermediate product for the preparation of the inventive Connections to use »

The term "strong proton acceptor" refers here and in claims to a substance that is capable of being a proton from the para position of the sterically hindered phenols or thiophenols split off, which are used to prepare the intermediate products described above and shown in formula V. Suitable, generally known proton acceptors are alkali hydroxides such as sodium and potassium hydroxide, alkali alkoxides such as Sodium and potassium methoxide and ethoxide and alkali amides such as sodium and potassium amide.

The method described is preferably ± n a solvent under an inert atmosphere conducted © as the solvent, any inert medium suitable which does not affect the desired reactions "can polar © © w ± and non-polar

309820/1052

Are used solvent "Generally Geraische of polar and 'non-polar solvents are used to _f to achieve at least a partial miscibility of the various Reaktionsfceilnehmer. For example, a mixture of '.fasser, Diuiethylsulfoxid and P ent at, hexane or heptane for carrying out the i _e action suitable. The inert atmosphere can be any oil that does not affect the reaction. The boquenist is worked under nitrogen.

The reactions are carried out at low to medium temperatures, ζ.13. at about 0 G to about 50 C and preferably at about 10 ° C to about hO ° 0.

if after oinom the fourth m er Jan ".1 of the iirf in'ij.mj · are procedures for the position described above and given in formulas I-IV Ester tier i / itiiiobcnsoesliure and the substituted üensole characterized in that the above as an intermediate described dithiobenzoic acid in the form of the liadical with zero until one equivalent of a proton donor is combined, wherein a third reaction product is obtained. This third reaction product is then reacted with two to one half equivalents of a precursor of the desired thiαsubstituenten.

The amount of proton donor with which that is present in radical form Intermediate product is combined is determined by the desired reaction product. If as a lieaktionsprodukt a Diester according to formula III above or a cyclopentylidenebenzene to be prepared according to formula IV above ', is the intermediate product not reacted with the proton donor The double salt is free and can be mixed with two equivalents

8A0 ORIGINAL 309820/1052

11 b I υ / ο

the precursor of the thio substituents are brought to implementation The precursor has only one reactive site or an equivalent is used if there are two reactive sites Owns. If a monoester is used as the reaction product Formula I and II are to be prepared above, the intermediate is made with one equivalent of the proton donor united. The product can then react with an equivalent of the precursor containing the thio substituent, if this Precursor has one reactive site, or it can be reacted with one and a half equivalents if the precursor has two reactive sites As in the case of the dihaloalkanes, from which the compounds of the formula II are prepared. The case that the precursor is a dihaloalkane in which the halogen substituents are on adjacent carbon atoms, is discussed below.

The term "proton donor" refers here and in the claims to a substance capable of donating a proton to the thiobenzoic acid radical. Suitable as a proton donor are mainly strong mineral acids such as hydrochloric acid, Sulfuric acid and nitric acid.

The precursors for the thio substituent are alkanes, hydroxyalkanes, Hydroxyalkyloxyalkanes, hydroxyalkylpoly (oxyalkyl) oxyalkanes and aralkanes which are substituted with at least one substituent that they are opposite to the dithiobenzoic acid radical makes you responsive. These substituents are usually halogens and preferably chlorine. The preliminary stages are with a Halogen group substituted, with the exception of the precursors that are used to prepare the Sster of the formula II and the dithiacyclopent-2-

"^'■":; ■■■■ "309820/105?

ylidenebenzenes can be used. The precursors for these two Compounders contain two halogen substituents. The addition the proton donor to the dithiobenzoic acid radical can be carried out at various temperatures, most conveniently it takes place at room temperature,

The esterification of the dithiobenzoic acid radical with the precursor of the thio substituent can also be carried out within a wide temperature range from about room temperature to about 100 ° C. or above. Preferably, the reaction is carried out in such a way that Dithiobenzoesäureradikal and precursor for the thio substituents are as combined at room temperature, is heated wprauf the reaction mixture with stirring to about 50 ⁰ C to about 90 ° C ·

The time required to carry out the reaction depends on the temperature, concentration, and so on. In general the reaction is complete within one to five hours if carried out in a favorable temperature range will·

It has been found that in the production of the bis-esters such as, for example, compound X from dihaloalkanes which carry the halogen substituents on adjacent carbon atoms, a large amount of the corresponding di-cyclopent-2-ylidenebenzene is formed.

Even if this statement is not intended to be associated with any stipulation, it can be assumed that daa is used in the implementation of one equivalent of dihaloalkane with one equivalent of Dithiobenzoic acid chemically formed intermediate as follows reacted:

r 30982Q / 10R?

-ίο-, ι'et lon A

Ki-

Rg. Jet ion B

-, --.— ^ j ₃ ,

r s-c'Bfo.

y-i

ft.

left

"* Y rf 'C V

As is easy to see, the possibilities of reduction are not limited to the problems shown above. Another l ³ rodiilct kanii a pole ^ mer with a carbon ens toff Soliwefel chain ssein, αϊ the Oxobenzolgruppen DER bofinden "& s are other Prodtucte conceivable.

Of this multitude of possible modules, only identified zv / ei, n ^: uali;.; H dio i'roduhte der ile · 'ctionon A and B above. The nlol.t: erei ii.; Te iieaktionsprodu; t, the production of which is described below in JJeifivjiel VII besoliriebon, results in the addition of a Jchi.iioi'cjl, \ / ie described below, a hiccup ₉ which is excellent ειΐε Ilochdruckschinierrmittel proves and also a high read'uuliiikait towards oxidative changes. "owns ·

30 9 820 / $ 10?

^BATH

, but the l'rodulct r-.us Ae: Iztlon Ii isolated above and a Jcii'iier.il «! i-yesefc :: fc v / ird, a mixture is obtained which does not have nearly as good properties as a high-pressure lubricant, like the mixture that .us your uncleaned .product! ι ο r [■; e; j divides v / urd e.

What is contained in the unpurified product and which gives lubricating oils their excellent properties is unknown. Without that should be setting a maximum here, can angenom; ien are that there is a synergistic effect of the combination of concerns bis-Jisters (reactive Λ) and the Dithiacyclofient-'i-ylidenbenüols (lieaktion Ii), or it could a third component that has not yet been identified may be responsible. Finally, a combination of these possibilities cannot be ruled out.

According to a fifth feature of the invention, lubricating oil blends contain in a predominant amount an oil of shear viscosity and an effective amount of a compound belonging to a group consisting of esters of ^ -hydroxy-dithiobenzoic acids, esters of 4-thiol-dithiobenzoic acids,!, ^ - Dihydro-l-oxo - ^ - dithiomethylene benzenes and 1, 'i-Dihydro-l-oxo -' + - (1, 3 ~ dithiacyclopent ~ 2-ylidene) benzenes, in which the ester and benzenes on the nucleus are alkyl substituents in both ortho -Positions to the hydroxy, thiol or oxogroup that sterically hinder these groups. According to the invention, the lubricating oil mixtures preferably contain a predominant amount of an oil with a lubricating viscosity and an effective amount of one or more compounds of the formulas I-IV.

SAD ORIGINAL

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- 46'-

The esters and benzenes are in the lubricating oil mixture in one Amount sufficient to give the oil the desired properties. This amount is in the range of about OjI percent by weight to about 5 percent by weight of the total mixture and generally from about 0.5 percent to about 3 percent by weight of the total mixture.

In general, solutions of the Egter and benzenes in oil are easily obtained to when the are oleophilic in the above formulas by R ", R ^ and R _6, groups represented possess ie average or longer alkyl chains such as octyl-1, decyl, Dodevyl, eicosyl and others, or if they have a higher number of oxyalkyl units in the hydroxyalkyl poly (oxyalkyl) chain.

It has been found that the hydroxyalkyl substituted compounds and the higher homologues tend to crystallize. In some cases, for example when using higher concentrations from 2 to 5 percent by weight of the total mixture, they are difficult to dissolve and crystallize in the oil occasionally from the oil. These crystallization problems are generally easy to solve by using a mixture of hydroxyalkylenes with different numbers of oxyalkyl units is used in the chain, such as a mixture of esters having about half the hydrox3> alkyloxyalkyl and hydroxyalkyldioxyalkyl substituents own.

The esters and benzenes can be added to the oil individually or as mixtures. For example, a mixture of two or more esters can be used. It can also be a mixture of

309820/1052

OftenJGfNAi

two or more benzo} enes or a Jeminch from iistem u id jjen- /-.olcn can be used. It should be pointed out that the Jjonaoles are certain double esterification products which are obtained in the synthesis of the lister, different hens are de-oiled from esters or. ·; ·! i'Uii-:; en obtained at the S ^ mtliese dci 'jei / eils ndcen connection. In general, it is most convenient to use simply obtained mixtures without attempting to separate the veri.) Indun ;; on zn.

Other additives can also be added to the mixture, in order to meet andex "e i ^ nctions than they are by the invention Esters and benzenes can be achieved, and also to the To reinforce the functions of these latter ",

These additives can be used in the oil in different amounts, to be present. It is usually found in oils used in an internal combustion engine The total amount of these additives should be used at about 0.1 to 15 percent by weight and preferably at about 0.5 to 10 percent by weight. The individual additives can be used in an amount from about 0.01 to 10 percent by weight of the total mixture are present.

These additives include ashless dispersant additives such as e.g. succinimides, hydrocarbylalkylene polyamines etc., corrosion inhibitors such as metal dithiophosphates etc., detergent additives like z.ü. Sulfonates, phosphonates, phenates, etc., agents for improvement the viscosity index such as z.JJ. Polyisobutylenes, polyacrylates, etc., agents for lowering the pour point such as e.g.

309820/105? «AD OR, G, na _L

Polymethacrylates, polyacrylamides, etc., extreme pressure additives as well other additives to achieve specific goals.

3chmierül e

The oils which are used according to the invention are oils with a lubricating viscosity from petroleum or of synthetic origin. It can be paraffins, esters, naphthenes, halogen-substituted hydrocarbons, asphalt products or combinations of these substances. Suitable oils typically have viscosities in the range 35-50000 SayboIt-seconds (S ^ft) at 38 ⁰ C (3 to 10,800 centistokes) and usually from about 50 to 10,000 S "at 38 ⁰ C (7.5 to 2.I6O centistokes ).

The following examples serve for a more detailed explanation, not but for the sake of change · the invention.

Example I - Oxidator B Test

The stability of an oil mixture to oxidative changes is measured using the time uerstoff for the consumption of a liter of S _a through 100 of the test oil at 17I ⁰ C g is required. For convenience, the test described herein uses 25 S oil and converts the results to 100 g samples. A catalyst with a mixture of soluble salts is added to the oil; it contains 95 ppm copper, 80 ppm iron, 4.8 ppm manganese, 1100 ppm lead and 4? ppm tin. The test can be extended to a total of 10 hours; the liters of oxygen absorbed during this time are measured. In addition, the viscosity of the oil is determined at the beginning of the test and after the 10 hours have elapsed. The rise

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is recorded as a percentage of the output value. In table I are the values given that are given for a singular of Oil blends were obtained in the oxidizer B test. The quantities of the individual additives are given as percentages by weight of the total allowance specified. The oil used in these tests is a neutral hydrocarbon T-oil purified by solvent refining with a viscosity of 480 Saybolt-Selconds at 33 ° C (10 4 centistokes).

COPY 309820/105?

TALL I

Oxidator D test

Ad - T xtxv the b »wt. / ui d ere 1 C. D. E. Life 0 "Recording Visc ._ τ " E-i-'f indu ic "VO Ge Additive "* ' 6th Hours for recording Liter / lO / UiS tie Ül V er 1 A. wx -.:h t percent 6th from 1 liter 0 ,, hours ^ ₀ ί S ° .Uo. 1 B. 6th 4.0 . 4.6 60 1 II ι 1 1 6th 4.1 4.0 64 2 III 2 6th 4.5 3.5 . 59 3 III 2 1 6th 3.4 ■ 1.7 16 Il III ρ 1 6th 7.6 1.8 18th 3 III 2 6th 7.0 1.8 23 6th III ρ 1 1 5 0.1 2.4 31 7th III 1 5 0.1 4 »7 2.5 41 . > in 2 5 0.1 5.5 111 0.5 ■ 5 0.1 '·), 3 ιό III 1 5 0.1 -, 6 11 VI 2 • »7 12th VI ever 5 0.1 o, 6 13th Vl 0.5.0 0.1 II VI 1 5 0.1 3.6 VIII 1 0.1 6.5 15th I. 2 3.4 16 XIj. ever 5 ο, ι 5.2 17th XII 1 / b 5 0.1 18th 1 1 5 0.1 .,,1 XII 1 5 0.1 6.4 19th IX 1 5 0.1 6.2 20th 2 0.5 5 0.1 4.8 21 O 1 1.9 22nd 3.5 23 F.

Other additives

A. B. C.

cc

te D. co

cn

P.

• ie

2,2'-bis (1-hydroxy-4-polypropylene-pliene 3'-1) disulfide, proζent in oil,

75 weight

2, 2 * -bis (l-hydr oxy-6-metlayl-4-polypropylenepla enyl) disulfide, 75 percent by weight in oil,

A polyisobutenyl succinimide produced by the action of a. Succinic acid inhydride of a polybutene (i-IBSA ^ 5 °) with an average molecular weight of about 95 ° uit Teti ^ atlthylenpciitaniii (TIiP ..) with a high ratio of TEP ui. to i! USA of 0.87; About 44 percent by weight of active additive in Ollösun ;;.

Terephthalic acid,

9th ^! t3 percent by weight of a porisobutenylsuccinide like that of compound C, but using a succinic acid. iltnis of TEPA to Ges.unt TIjjS ^ to 0.50, and 0.7 percent by weight of terephthalic acid,

Ice (3, 5-di-t-butyl-4-hydrox3 '--- /: je: i3'-i) ;: ieth3'lcn - a commercially available . jitioxyd.-jis, because brd serves as the substance of the above experiments

• ': tion - \' ro (] ut get a-.is .Jeis] ^ icl VII below.

IAO ORIGINAL

COPY

From "lon the above results it can be seen that the inventive oil mixtures against oxidative changes at least as good and generally better resistance like the comparison mixture.

Example II - P a ^ ex-Hpchdr u jjktest

The utility of an oil mixture under high pressure conditions can be determined by this test. The FaIex machine is manufactured by the Pnville-LeVnly Corporation of Chicago, Illinois. In this test, two opposing, solid, prismatically shaped blocks are pressed against each other and against a steel shaft rotating in between by means of a nut knaeker arrangement of lever arms. The rotating shaft is driven by a suitable device using a brass shear pin. At a certain temperature, the block and test specimen are immersed in a vessel with the detergent to be tested. The machine operates at 290 rpm and the test specimens break under a load of 36 kg. During the test, the load between the prismatic blocks and the pin is automatically increased until the plague eats. The point at which this occurs is indicated by the shearing of the brass pin holding the rotating shaft. The load when breaking in kg is used as a quantitative hatred for the high pressure properties of the ulcer. In this test, mineral oils provide values of 272 to 408 kg. oils with medium high pressure additives fail at h53 to 907 W; and very effective high-pressure additives allow loads over 13 <10 kg. The results of the tests with the oil mixtures according to the invention are shown in Table IIj "WiOUCr ₁₁ C _1. "

309820/1052

2252Q76

'i? ... J.j

at

Ul no

1 4o.;, 4yO 1246 IO 713, 725 2 453, 4 ') a 11 544, 500 3 1676, 1676 12th 509, 539 4th 490, W) Z 13th 715, 725 539, 50 ') 14th 509, 509 6th 1133, 1631, I) 5OO, 509 ,, 7th 534, 634 20th 2038, 2033 - 8th 1314, I4o4 21 1800, 1880 9 453 453 23 408

See Table I as well as the JJ ¹ U £ .13110 below regarding the composition of the oils,

A load of 203O 1 <; isb the M; .xir.11 im, the mi b der. at

tests used Fnlex machine can be achieved _o No seizure occurs under this maximum exposure.

In the above Falex test, all of the mixtures according to the invention showed acoustic pressure properties which were similar to those of the comparative standard no. 2 ') ,',. Are corpse and in many cases clearly superior. l-iif5ch No. 20 showed particularly hex 'outstanding shank'. 'Ii. The necessary tests of the reaction product from Jlei.jjjiel VU with other ad iltivkombinatIonen are in Table JID

0
ü

24

FaI ex-Uo chdrxickt it t

JjI _- Ho.
26th

21

0.1

> 1 1 MeIaS butig- _; ii '/> 44 2038 Ln kg 'ί'Ί
_) i-.L 2030

21

ο, ο4
ό

0.25 0.25 11

1 1

6IP. II33 .317 1L55 566

6 «57 1133 ^ 30 974 '612

3 0 9820 / 1OB?

"'■■> ■ ■■ _

'"In (ion same Noiifcr UiI -ι it ο Liier viscosity of hSO S" (lo't Contiü bolce.) As the obl.on examples.

1 Ii.Ln. According to the composition of the additives

C mid D,

The additives are .ils percentages by weight of the total

mi s ο! κ in; , -. uigegeb un ·

Additive F - like iS, but olme terephthalic acid. Additive D - tetrapropenyl succinic acid

'Ieiktioiisprodukt from l; eispiol VII

The reproduced in Table HD results iieigen that the de ict Loiifiprodukt IIIs Example VII, both alone and in combination with other additives, the Hochdruckeifjenschaften a Schiileröin vorbessert "It should be noted that P ro bo fίο, 2V> _{f is} the only additive G, That is, an acidic compound, which contains, does not behave more favorably than gruadol, which, as above mice füberi, proves to seize up at about 27- "2 to 408 kg. On the other hand, sample No. 30 showed only the heat product It contains from Example VII, Ilochdrucke properties at IJelastun / you, the approximately ^r 10 I't'ozont iibiiX 'those of the base oil lagiiri, i; iit odor without additive G ₁₁ Bemorkensi / erterwelse showed the oil No. 2 ^e j, 27 and 29 »(Ho contain both the induction product of Example VII and: iich an acidic compound (xLdditive X) or G), Ilochdrucke properties under loads that were considerably higher and in a case (ul No. 25) up to Belcistungsf ; renae der MnschLno g iti,; on _#

ni ',:! III - Lagorko rt osions to s t

Additives Scluiiierö In Güns i; grant ije iSigtmsciuif ttm may _o ite on the other S not have scli.Ldli hon l / iiicungen "To be avoided must before iLloni this corrosion of engine parts, especially those of NichteisentoLie that the UEL in Touch! Common ,, lüLue Korro.s Lon servant kind, which by a single

3 0 9820/1057.

Ad / · i ti ν is advertised by. Immersion of lead and Ku ^ f "J ^-1 S-ti eif en olmisclimig measured in the test, i / oboi these 20 hours wirdo ΰ kept at a temperature of 146 By" .Ziegen the strips of the nominal thread is djin OHTS loss Certain copper sticks are also washed with liquid liquid to remove deposits of copper compounds, and weighed again. The results obtained from testing various combinations of additives according to the invention are listed in Table III .. Here, too, the neutral oil with a viscosity of 400 S "was used as the green oil.

1 TABLE III lead test corrosion lead 2 Lagerlcorrosioiio 2.6 copper 2.6 3 Corrosion ^v 2.5 Ol Ho. I2 / 29 11.8 No. ' 4th ^L copper ³ 4.3 ⁹ h 33/54 1.9 5 12/29 1.9 9-A 92/123 1.2 6th 3/21 103.1 10 9/20 1.4 7th 14/23 1 x 3.3 11 39/52 Oi £ 8th 92/120 4.9 12th 89/107 0.3 10/23 20.1 13th 16/33 0.1 l / S 14th 11/15 0.2 IO / 3O ²⁰ 4 5/13 IO9 / 123 20-A ^V

See the previous examples regarding the composition.

ο
Reported as loss in milligrams .i.

Specified as B / A, D = copper loss before ^{the KCN-T} -W; isolie and A = copper loss after the KCN-TJUs; hc.

The same composition as 0 or 20, but without additive D.

True, the above numbers, especially the results for the ülen No, 9, 9 -. *, 2C and 2O-λ k a conclusive proof of the It is necessary to have a mild organic acid in the oil.

* AÖ

309820/1052

is essential to retard non-ferrous corrosion, however on the other hand, the results prove that the presence of such an acid does not entail any adverse effects brings. This is desirable because the presence of these acids increases the extreme pressure properties of the lubricating oil, as shown in Table IIB above.

The following examples IV, V and VI show the listening position of three compounds which are suitable for use as antioxidants in extreme pressure additives in the mixtures according to the invention suitable. The preparation of the three compounds is the same up to the point of that in "General Preparation of Additive Intermediates" at the end is the speech.

309820/105?

General manufacture of intermediate additive products

2,6-Di ~ t-butylphenol (20.6 g, 0.1 mol) in dimethyl sulfoxide (50 ml) is placed in a 500 ml three-necked flask equipped with a guide, thermometer, nitrogen supply, dropping funnel and reflux condenser. A solution of potassium hydroxide (13.2 g, 0.2 mol) in water (15 ml) is prepared, cooled and diluted with dimethyl sulfoxide. This solution is added to the phenol solution with stirring under nitrogen. The solution is with the aid of an ice water bath to 10 ° C - 5 and cooled (7.6 g, 0.1 mol) with stirring carbon disulfide offset _f 'wherein the temperature is maintained at 10 0th After the addition is complete, the mixture is stirred for a further 30 minutes at 10 ° C. It is then no longer cooled and the stirred solution is brought to room temperature. At this point synthesis continues with the unisolated intermediate as described in Examples IV, V and VI below.

Example IV - Preparation of Compound III - 3,5-Di-t-butyl- 4-hydroxy-dithiobenzoic acid n-octyl ester

Concentrated hydrochloric acid (10 ml) is slowly added with stirring to the non-isolated intermediate product prepared as described above, then 1-bromooctane (19> 3 St 0.1 mol) is added. The mixture is stirred for a further hour at room temperature. The temperature is ^v for one hour at 70 C - increased 10th The reaction mixture is then cooled and poured onto ice water (500 ml) with stirring. The aqueous mixture is extracted three times with 200 ml of ether. The combined organic extracts are dried over anhydrous sodium sulphate and the solvent is circulated in vacuo.

309820/1052

? 252Q76

damper expelled. 35t ^ S of crude product is obtained, which is suitable for use without further purification. Recrystallization of part from a hexane mixture gives a red crystalline substance.
Elemental analysis: sulfur - found * 16.3 <f> \ calculated! ± 6.2

Example V - Preparation of Compound XII - 1 _f-4-Oüiydro Loxo-2, 6-di-jb-butyl-4-dimethyl thiomethylenbenzol

To the unisolated intermediate prepared as described above, iodomethane (28.4 g, 0.2 mole) is slowly added with stirring. The mixture is stirred for a further hour at room temperature and then a Sturide is heated to 70 ° C. The reaction mixture is cooled to room temperature, 200 ml of water are added, and the mixture is then stirred for a further 15 minutes. The aqueous mixture is extracted three times with ether (250 ml). The combined organic extracts are dried over anhydrous sodium sulfate and the solvent is driven off on a rotary evaporator * This gives ₉ k g of crude product for 2 hours, which can be used without further purification.

Example VI - Preparation of Compound IX - Bis (3,

butyl-Jf-hydroxy-dithiobenzoic acid) methylene ester

Diiodomethane (l3 »4 St 0.05 mol) is added to the non-isolated intermediate product, prepared as described above, and the mixture is stirred at low temperature for another hour, then heated _{to 70 ° C + 10 ° for one hour} Stir poured onto ice water (500 ml)

309820/105?

- 27 - 2252Q76

The aqueous mixture is extracted three times with ether (200 ml). The combined organic extracts are dried over anhydrous sodium sulfate, filtered and the solvent is removed on a rotary evaporator. The solid The reaction product is dissolved in a hexane mixture and a saturated solution is prepared. The solution is in chilled in a refrigerator. The mother liquor is separated from the Crystals are decanted and the crystals are taken up in 750 ml of hexane mixture. The volume of this second Solution is reduced to about half and the solution is cooled, which leads to crystallization. The so obtained Crystals are suitable for use as a shear oil additive. "

Example VII - Preparation of Compound X - Bis (3,5-Di-j; -

butyl-4-hydroxy-ditliobenaoic acid) ethylene ester

2,6-Di-t-butylphenol (61.6 g, 0.3 mol) in dimethyl sulfoxide (75 ml) and Ileacan (75 ml) are placed in a 1 l three-necked flask equipped with a stirrer, thermometer, nitrogen supply, dropping funnel and reflux condenser. brought in. Prepare a solution of potassium hydroxide (39.6 g, 0.6 mol) in water (45 ml), cool and dilute with dimethyl sulfoxide (25 ml). This solution is added to the phenol solution with stirring under nitrogen. The temperature of the solution is kept at 30 ° C ί. The solution turns green. At the same temperature, carbon disulfide (23 $ 0.3 mol) was added with stirring. The stirring was continued for one hour at room temperature, the reaction mixture turning a deep red color. While the temperature is further kept at 3O ⁰ C, concentrated hydrochloric acid (3 ° mL) and then ethylene dichloride (l4,8 g, 0.15 mole) is first added. The reaction mixture is on for one hour

309820 / 10S?

Heated 70 ° C ί 10 ° and then cooled to * 10 ° C. Distilled water (300 ml) was then added and the reaction mixture was stirred for a further five minutes. The mixture is separated in a separating funnel and the aqueous phase obtained is treated with distilled water (500 ml), followed by extraction three times with CHEVRON Thinner 250 * (600 ml). The combined organic extracts are washed three times with water (70 t) ml) and dried over anhydrous sodium sulfate. The organic phase is filtered and the volatile constituents are driven off in vacuo on a rotary evaporator. Will receive 73 "^ S of a product that is suitable without further purification for use.

The subsequent analysis of the reaction product shows that there are significant amounts of the compound X, a bis-ethylene ester, and the compound XVII, a dithiacyclopentylidenebenzene, whose structures could be confirmed by nuclear magnetic resonance spectroscopy.

Compound XVII, the dithiacyclopentylidenebenzene, was isolated and tested in the oxidizer B test and in the Falex high pressure test. the results obtained were not as good as those obtained with the crude reaction mixture as a lubricating oil additive *

ClIEVROJi Thinner PJjO is a water white, high aniline point petroleum gasoline sold by the Standard Oil Company of California.

OW fNSPECTED

309820/105?

Claims (1)

Claims \ »J Compound, characterized in that it belongs to a group consisting of the following substances: (1) Esters of 4-hydroxy-dithiobenzoic acids with alkyl substituents on the nucleus in both positions ortho to the hydroxyl group, which sterically hinder this hydroxyl group; (2) Esters of 4-thiol-ditliobenzoic acids which have alkyl substituents on the nucleus in both ortho positions to the thiol group, which sterically hinder this thiol group; (3) 1, ^ -Dihydro-l-oxo - ^ - dithioinethylene benzenes, the ani nucleus Carry alkyl substituents in both positions ortho to the oxo group, which sterically hinder this oxo group, and (k) 1, ^ - Dihydro-1-oxo - ^ - (1,3-dithiacyclopent-2-ylidene) benzenes which have alkyl substituents on the nucleus in both positions ortho to the oxo group, which sterically hinder this oxo group. 2. A compound according to claim 1, characterized in that it has one of the following formulas; 309820/105? where mean: (1) R ₁ and R each represent an alkyl group which sterically forms the adjacent hydroxy, thiol or oxo group. with special needs; (2) R_, Rh and R- each alkyl, hydroxyalkyl, hydroxyalkyloxyalkyl, Hydroxyalkyl poly (oxyalkyl), aralkyl or aryl} (3) R / r is an alkylene group; (h) X is oxygen or sulfur; (5) Y is hydrogen or a metal cation and (6) R «is hydrogen, alkyl or aryl. 309820/1052 3 · Connection according to claim 2, characterized in that (1) R. and R _{p are} each branched lower alkyl and (2) X is oxygen. k. Compound according to Claim 3, characterized in that: (1) R- and H are each branched alkyl containing k to 10 carbon atoms; (2) Ro »% and R- each alkyl containing 1 to 20 carbon atoms, a hydroxyalkyl containing 2 to 5 carbon atoms, a hydroxyalkyloxyalkyl containing k to 10 carbon atoms, a hydroxyalkyl poly (oxyalkyl) containing 2 to 5 Carbon atoms in each alkyl radical and containing 2 to 5 oxyalkyl units, aralkyl which contains 7 to 8 carbon atoms or aryl which contains 6 to 7 carbon atoms; (3) R ^ is an alkylene group containing 1 to 8 carbon atoms and (4) R _{7 is} hydrogen or eiji lower alkyl. 5 · compound, characterized in that it has the following formula owns: 309820/105? 225207R where mean: (1) R ₁ and R ₂ each represent an alkyl group which sterically hinders the hydroxy or thiol group; (2) X oxygen or sulfur and (3) Y is hydrogen or a metal cation. 6. A compound according to claim 5 »characterized in that (1) R 1 and R 2 are each branched lower alkyl and (2) X is oxygen. 7. A compound according to claim 6, characterized in that R ^ and Rp each represent a branched alkyl containing h to 10 carbon atoms. 8. A method for producing a compound according to claim 5, characterized in that (a) about one equivalent of a compound of the formula XY wherein R- ,, Rp, X and Y have the meaning given in claim 5 have, is combined with about two equivalents of a strong proton acceptor, and (b) the reaction product obtained is reacted with about one equivalent of carbon disulfide. 9 · The method according to claim 8, characterized in that daP> (1) R ^ and R2 each represent a branched lower alkyl, ■, OMQiNAL INSPECTED 3 Ü 9 B 2 0/1 Π S '? (2) X means oxygen and (3) an alkali metal hydroxide, alkali metal alkoxide, as the proton acceptor or alkali amide is used .. 10. The method according to claim .9, characterized in that (1) R ₁ and Rp each represent a branched alkyl containing k to 10 carbon atoms and (2) an alkali hydroxide is used as the proton acceptor will. 11. A method of making a compound according to claim 1, characterized in that (a) a compound of the general formula XY ·. (1) R ^ and Rp each represent an alkyl group that is adjacent to the Hydroxyl or thiol group sterically hindered; (2) X oxygen or sulfur and (3) Y mean a metal cation, is combined with 0 to 1 equivalent of a proton donor, (b) the resulting reaction, product with half to two equivalents of a haloalkane, α-halo-u> -hydroxyalkane, α-halo-uh-hydroxyalky 1-oxyalkane , α-halo-tu-hyd-roxyalkylpoly (oxyalkyl) -oxyalkane or haloaralkane is reacted. 3G9820 / 10K? 12. The method according to claim 11, characterized in that (l) R. and H ₀ each denote a branched lower alkyl and {?.) X denote oxygen. 13. The method according to claim 12, characterized in that ίϊ_ and H ₀ each denote a branched alkyl which contains 4 to 10 carbon atoms. l4. Process according to claim 13 »characterized in that (l) the values of 4-hydroxy- and 4-thiol-dithiobenzoic acids have the following formulas: XV (2) the 1,4-dihydro-l-oxo-4-dithiomethylene benzenes the following Own formula: 309820 / 10K? (3) the benzenes have the following formula: 0
R, " iv Kf-C - CR, where mean: (a) R_, R, X and Y are the same as defined above; (b) R, Rj- and R- each alkyl, hydroxyalkyl, hydroxyalkyloxyalkyl, Hydroxyalkyl poly (oxyalkyl), aralkyl, or aryl; (c) R, an alkylene group and (d) R “is hydrogen, alkyl or aryl, _etc. 15 · The method according to claim 1H _t, characterized in that: (1) R, Hr and Rk are each an alkyl containing 1 to 20 carbon atoms, a hydroxyalkyl containing 2 to 5 carbon atoms, a hydroxyalkyloxyalkyl containing k to 10 carbon atoms, a Hydröixyalkylpo Iy (oxy alkyl), the 2 contains up to 5 carbon atoms in each alkyl radical and 2 to 5 oxyalkyl units, aralkyl which contains 7 to 8 carbon atoms or aryl which contains 6 to 7 carbon atoms; (2) R5 is an alkylene group containing 1 to 8 carbon atoms and (3) R1 is hydrogen or lower alkyl. 309820/10 B? OffiOrtNAL INÖf ECTEO 225-076 l6. A method of making a compound according to claim 1, characterized in that (1) (a) about one equivalent of a phenol that has alkyl substituents on the nucleus contributes to the hydroxyl group in both ortho positions, which sterically hinder this hydroxyl group, with (b) about two equivalents of a proton acceptor are combined to obtain a first reaction product will; (2) the first reaction product at about one equivalent Carbon disulfide is reacted, with a second reaction product is obtained; (3) Combining the second reaction product with about one equivalent of a proton donor, with a third Realctions product is obtained, and (h) the third reaction product is reacted with about one-half equivalent of a dihaloalkane containing at least two carbon atoms in which the halogen substituents are on adjacent carbon atoms. Method according to claim 16, characterized in that an alkali hydroxide, an alkali alkoxide or an alkali amide is used as the proton acceptor, an inorganic acid is used as the proton donor and a dichloroalkane with 2 to 30 carbon atoms is used as the dihaloalkane. 18. The method according to claim 16, characterized in that »that the proton acceptor is an alkali hydroxide or an alkali alkoxide, an inorganic acid as proton donor and a dihaloalkane a dichloroalkane with 2 to 8 carbon atoms is used will. 309820 / 10B? OWOINAL INSPECTED 19. The method according to claim 16, characterized in that that as a proton acceptor an alkali hydroxide, as a proton donor an inorganic acid and as a dihaloalkane 1,2-dichloroethane can be used. 20 lubricating oil mixture which mainly consists of an oil of lubricating viscosity and containing an effective amount of an additive, characterized in that the additive is a compound according to claim 1, 2, 3 or ¹ J. For Chevron Research Company (Dr. H. ^U J. Wolff) Lawyer ORIQINAL JNSPECTSO 109 820/105?