DE1594584A1 - Lubricant mixture with improving additive mixture - Google Patents

Description

P 7431 \ CH Milnohe ?, dan 28 »May 1965

SHEIIi IHÜERHATIONAL RESEAfiCH MAATSCHAPPIJ NoVo, The Hague / Hol3

"Lubricants with improving additives tofigöiaiöch"

Priority, January 29, 1964 / Ü3A Registration number 371 184

The invention relates to an improved lubricant mixture. In particular, it relates to an additive mixture for a Lubricating oil and a lubricant composition which is a lubricating oil and Contains additives.

GeaÄi an embodiment of the invention is eioh a Zueetegemieoh that has a cyclieohee amine as well as a sale of one aliphatic amine with at least β carbon atoms and containing a Hnlogen-C ^^ - alkylphosphonic acid

Another embodiment of the invention relates to a Schaiermittelgemieoh, which is characterized by daü it is a bohaierül and as an additional mixture an oyollaohea aein «owle a salt of an aliphatic amine having at least β carbon atoms and a tialogen-C ^ -Alkylphoaphonic acid contains

CoheitraitteIgtmioch can O, Ol - 10 wt. ^, Vorzuewtist

Ο, Οί - 5 0 · * · ^ 'des oyoliBohtn contain amines «At Vtrwtndunf

■ ύ 00M32 / UU ^

A mixture of cyclic amines refers to this amount on the total amount of cyclic "amine"

The cyclic amine can contain an aromatic radical (ζ.B ₉ a benzene or naphthalene residue) or a heterocyclic radical (ζ “Bo a pyridine, quinoline or diazine radical).

Examples of suitable Aaine are phenyl-beta-naphthylamino; Dielpha-naphthylanine; Di-beta -naphthylamine; di-alpha, beta-naphthylamine; Triphenylamine; Diphenylnaphthylamine; 2-aminopyridine; 3-aminopyridine; 2,6 ~ diaminopyridine; 4 _f 4 '~ Dipyridylamini phenyl-2-pyriaylamine; Naphthyl-2-pyridylamine 1-4 aminoquinoline; and phenyl 3-ohinclylamine. Preferred amines are phenyl-alpha-naphthylamine; ^! xäi.Irii 2,2 ^< -dipyridyl-amine and 4 ^; -Aminopyridine.

The Sohmiermittelgemisch may 0.005 -. 5 6EW ^ _t preferably 0.01 - 5 wt. $ Of the salt contained. The weight ratio of the salt to the cyclic amine can be 0.01 / 1 to 10/1, preferably 0.01 / 1 to 5/1 . These amounts relate to the total amounts of the salt and the olefinic amine, if the cooking agent mixture contains more than one salt and / or amine.

The salt can be derived from one or more aliphatic amines derive. Such an amine can be primary or secondary Cg, Q-, preferably C ^ -j * alkyl mono- or polyamine. The AsIn can have a tertiary alkyl group »see B. "in· Polyisobutylene and / or polyprop} lineruppt. Examples of amines old tertiary alkyl groups are I, lt3,3-T «trastthylbutylamine

BATH ORIGINAL

methylpentylamine and 2 _i 2,4,4f6 _f 6-hexamethylhexylamine _o

Other examples of such an amine are described in US Pat. No. Hr ₀ 2,606,923 and 2,611,782. These include tert. Tridecylamine, Ieoheptyldiäthyloarbinylamin and Iboootyläthyl-propyloarbinylamine. Such amines are available under the trade name "Primene". Further examples of suitable amines are diamylamine; DihejyLamin; £ i (2-ethylhexyl) amine; Diootylamine; Dideojl-amine; Didodecylamine; Ditetradecylamine; Dihexadeoylamine; Siootadeoyiamine; Dibromodioctadeoylamine; Ieopropylolfefylamine; Dirioinolylamine; Butylrioinolylamine; Butyl-2-

amine; Silaurylaaini methylolamine; Ethylootylamine; leoamylhexyl- • min * Didyclohexylamine; Sicyclopentylamine; Cyclohexyloctylamine;

Cyclohexylbenaylamine; Beneyloctylamine; Ben £ yl-2-ethylhexylamine; AllyloctyJ-aain; Dodeoyl-2-ethylhexyl-amine; (l-leobutyl-3-methyl-

butyl) i-5v5,3-r * ethyloyolohexylaiain; I) i- (1-ieobutyl-3-oethylbutyl) amine; Ä-n-Dodeoyldiäthylenetriamiii; Hn-tetradecyldiethylenetriaaine; Ootylethylene diamine; I-2-Xthylhexyl-H-hexadeoyltriethylenetetraiaine; Heptyltrisethylene-diaJiin} H-tetradeoyltripropylenetetramine; H ₉ N'- '. Diallyltrieethylenediamine and 3-Htxyl-morpboline. _ ..

Aain can also contain other non-reactive groups in the carbon chain, such as amide or carbon groups. ■ '- ^v

All halo-C ^ -alkylphoephone acid is primarily one Halogtn-C ^ grAlkylphoephone acid Y used. I can do one or dibalogen-C ^ -alky! phosphoric acid. Pie acid · can The following general formula is represented by «ardent

Il

RP- (OH) ₂

in which R is a mono = to perhalo-C ^ .- alky! group. Preferably the acid contains at least one halogen atom bonded to the alpha carbon atom. The dialogen atom can be bromine or fluorine, preferably it is a chlorine atom.

Examples of the acids are:

Monochloromethylphosphonic acid; l-monoohloräthyl-phoephonic acid; 1,1-dichloropropylphöephone acid; Ferrous ethylphosphonic acid; Diohlomethylphosphonic acid; Perehloromethylphosphonic acid; Monobromomethylphophonic acid; 1, l-chlorobromopropylphosphonic acid j Dibromomethylphosphonic acid, monofluoromethylphosphonic acid, and 1,1-difluoroethyl-phosphonic acid.

The salt can be obtained by direct neutralization of the dalogen-C ^, -alkylphoephone acid or acids with a stoichiometry Lienge of the aliphatic amine or amines can be produced.

The neutralization proceeds at normal or moderately elevated levels Temperatures and can in the presence of an inert dilution alttele or Lb'aungi means (e.g. a coal waea toffee, Xthers or ketones). Making dee Salt is described in U.S. Patent 2,858,332. That Salt can be modified by an alkali metal as described in US Pat. No. 3 U2,267. So there can complete amino salt of a phoephone acid are produced, which then in a low-boiling solvent with an »Al-

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BATH ORIGINAL

Potash metal hydroxydicarbonate or alcohol is treated, so that in the salt an amino group through an alkali metal atom is replaced »Preferred alkali metals are sodium, potassium and lithium.

As the lubricating oil, a mineral or, preferably, lubricating oil can be used synthetic lubricating oil can be used. Examples of synthetic Lubricating oils are aliphatic esters, silicones, polyalkylene oxides, polyphenyl ethers, fluorinated hydrocarbons, polyolefins and phosphoric acid esters. Examples of silicones are methyl silicon, Methylphenyl silicone and methylohlophenyl silicone. Examples for polyalkylene oxides are polyisopropylene oxide and polyisopropylene oxide dieters and polyisopropylene oxide diesters. To the fluorinated Hydrocarbons include fluorinated UIe and perfluorinated Hydrocarbons.

The synthetic cooking oil can be a simple ester (reaction product of a monohydroxy alcohol and a monooarboxylic acid), a polyester (reaction product of an alcohol and an acid, one of which has more than one functional group) or a composite ester (reaction product of a polybasic carboxylic acid with more than one alcohol or a polybasic Alcohol with more than one acid). The synthetic cooking oil can exist as a mixture of such substances e.g. contain a major proportion of a composite ester and a minor proportion of a diester.

8AD ORIGINAL

008832 / 15U

the synthetic lubricating oil is an ester of a ^ "ρο *""preferably C,. ^ - alcohols and a Gx ^ O" ^{9 vor2U} S " ^{SWo: S} - ^8e ^ a in -carboxylic acid (preferably an aliphatic carboxylic acid).

Examples of esters ale synthetic lubricating oils and ethyl palmitate, ethyl laurate; Butyl stearate; üi- (2 ~ ethyihexyl) -bacate; Di- (2-ethylhexyl) -elate; Ethyl glycol dilaurate; Ia- (2-ethylhexyl) phthalate; Di (1,3 - = - methylbutyl) adipate; Di- (1-ethylpropyl) = - a2elat; Diisopropyloxylate; Dicyclohexyl sebaoate; Glyceryl tri-n-heptoate; Di (undecyl) azelate; and ¹ l ⁱ etraäthylenglycol-di- (2-äthylencaproat) and mixtures thereof. A preferred mixture of esters consists of 5-80% by weight of Bi8 <- (2,2,4-trimethylpentyl) azelate and 20-50% by weight of 1,1,1-trimethylpropane triheptanoate

Preferred synthetic lubricating oils are the esters of Monooar bonic acid with 4-12 carbon atoms and polyalcohols, e.g. Pentaerythritol, dipentaerythritol and trimethylolpropane.

Examples of these esters are pentaerythritol butyrate; Pentaerytebrittetrabutyrate; Pentaerythritol tetraväleratj pentaerythritol tetraoaproate; Pentaerythritol dibutyrate dioaproate; Pentaerythritol butyrate caproate derivative; pentaerythritol butyrate trivalate; Pentaerythritol butyrate trioaproate; Pentaerythritol tributyrate caproate; mixed saturated fatty acid esters of pentaerythritol; Bipentaerythritol hexavalerate; Dipentaerythritol hexeoaproate; Dipentaerythritol hexaheptoatj Dipentaerythritol hexaoaprylate \ Dipentaerythritol tributeratoaproate; Dipentaerythrittrivfflerattrinonylat, mixed Diperi ^ isrythritbexaeeter von C ^^ iQ-IfiiiteUuren and Trimethylolpropaneheptylat. Pentaerythritol

009832/1614

Λ)

esters of aliphatic C, ^ 2 ~ ^{monocarboxylic acids and} excellent synthetic animal oils. They are commercially available from the Heroules CuheAioal Company,

The esters used in synthetic lubricating oils can be produced by a simple reaction of the alcohol and acids in the proportions suitable for the production of the desired product. Until conversion takes place preferably in a solvent (fc "B. An aromatic hydrocarbon) and the equivalent of a catalyst (a <, B. HOl, HF, HBr, H ₂ SO ^, Η * ΡΟ _Λ , 0001a or Bf *) instead. The preparation of some esters is described in the US Patents 3,038,859 and 3,121,109

Examples of monohydric alcohols sstar used to prepare the synthetic ale Sohmierüle are suitable are methyl, butyl, Ieoootyl> _t * and Dodeoyl Ootadeoyltlkohol. Also oxo alcohols, which are produced by converting olefins with carbon dioxide and water, can be used Examples of such alcohols and 2,2,4-trimethylpentanol-1 and 2,2-dimethyl propanols

Examples of polyhydric alcohols used in the production of the as

eytithetiBohe ßohniieröle used Beter are suitable, lind liialkohole, ζ, Β. 2-ethyl-1,3-hexanediol, 2-tropyl-3 _f 3-h «pt» ndiol,. 2 «Butyl-l, 3-butanediol, S ^ -Dimeöityl-l / i-butane diol, and polypropylene glycols old a molecular weight of 100 - 300 can also alcohols having 3, 4 _t 5 or more per molecule used Hvdroxylgrurmen

BATH ORIGINAL

are, they are preferred, are examples of these alcohols Pentaerythritol !, dipentaerythritol and 1,1,1-trimetbylolpropane. Ee Mixtures of alcohols can also be used.

Examples of carboxylic acids which are suitable for producing the esters used as synthetic lubricating oils are monobasic and dibasic aliphatic carboxylic acids, for example butyric acid, valeric acid, sebacic acid, azelaic acid, suberic acid, succinic acid, caproic acid, adipic acid, ethyl suberic acid, diethy / adipic acid, oxalic acid , Malonic acid, glutaric acid, pentadecanedicarboxylic acid, egglycolic acid, thiodiglycolic acid, acetic acid, propionic acid, capric acid, lauric acid, palmitic acid and pimelic acid and mixtures of aliphatic C ^ _ ₁₂ »mono-carboxylic acids.

The invention will now be illustrated by the following examples which show some compositions for lubricants according to the invention indicate.

Example "I '■...

60wt Bie ^ ~ (2.2 _v 4-trime1ihylpentyl) ~ azelate) base oil 40Gewji 1,1,1-Trimethylpropantriheptanoat) ^"A * + # lGew phenyl-alpha-naphthylamine

+ O _D 2Gew5C of the salt of liked primary C _{1R pl} -tert.Alkylemi

¹⁰⁴ nen and monohydric methylphosphonic acid

009832.'15U

Example TI

60Gew $ C. ₇ aliphatisoher C. ,, - monocarboxylic acid star) of pentaerythritol)

4QGew # C ^., ^ Acid esters of dipentaerythritol) + IGewji diphenylamine
+ 0 _v 2Wew # of a salt of mixed primary C-, □ _n

Alkylamines and monochloromethylphosphonic acid

Example III

Base Oil "B" of Example II '+ Weight # 2.2 · -

Dlpyridylamin + 0 _o 2Wew ^ of a salt of mixed · primary C _{18a & 2.} * Tert -alkylamines and mono-chlorathylphosphonic acid

Example IY

Base Oil "A" of Example I + IGew ^ 4-aminopyridine + 0> 2Ge »3L of a salt of mixed primary G ^ q ^ a. A3 kylaminen ur.d 1 _f 1 -Diohloräthylphosphonicäure

Example Y

Base oil "B" from Example II + 1 weight # Diphenylamine + _ "" SrS ^ -Dipy.ridylaßiinfeines üaltes of mixed

f Aliiylaminen and Monoohlorm.e.tby.lphoephon-0 »0075Gowji Kupierdibutyldithiocarbamat + '0 * 001 Gtwjt ink silicone oil

Example VI

Baois Oil "B" from Beieplel Ii + iGew? I Phenyl-elpba-naphthylamine

one thing be it from gtiuiochttn primary. text. AlkylaiQinen and Monoohlormethy.lphoephon- and O.O575'Jew ^ Benatoijriazol + 0 _o Ü01Gew # one

BATH ORIGINAL

009832 / 16U

The benefits of using a combination of the salt of an aliphatic amine and a halogenalkylphosphonic acid together with a cyclic amine are described below.

It has been found that the interaction of the salt with the cyclic amine increases the resistance to oxidation. This effect is explained duroh the following Table I, which shows the results of a Luftoxydationstestes at 204 ⁰ C.

In this test, air is passed through a sample of 20 g at a rate of 70 ml / min, which acts as a catalyst £ 0.002 copper and 0.002 * iron (as soluble octoate) contains. The base resisting oil (Oil "E") is made up of 60% by weight of aliphatic C ^ »-Monooarboxylic acid esters of pentaerythritol and 40 Gew.J (γοη aliphatic monocarboxylic acid ester »des taerythrite

Table I.

composition Induction »Ztit, Hours" oil E + weight # Phenyl-alpha
naphthylamine
oil E + O.2Gsw? 6 Sale ¹¹ A ¹¹ O
Oil E + lGtw # Phenyl-alpha-
naphthylamine + 0.2 wt ^
SaU "A" • rsttr passage BWtiter DUrohganj 25th
1
51. 24
46

x) Sal "" A "int" in mixed "SaIs of Monqchloraethylphoephon sMurt and a mixture of priorities

00II32 / 1IU

BAD ORiGINAL

The induction time dee stabilized by a cyclic Amiη Bass oil doubles by adding salt eich proves to be an ineffective antioxidant without the amine.

Further evidence of the beneficial effects is provided by the results of the oxidation corrosion test shown in Table II below. The oil ⁿ F ", / consisting of 95 wt # of aliphatic C.« monocarboxylic acid esters of pentaerythritol and 5 wt # of aliphatic Ce ^ Q monocarboxylic acid esters of dipentaerythrite) is used alone, with the salt and the cyclic amine in each case as well with the combination of Sale and Amin subjected to a read similar to that described in Federal Test Method Standard No. 791 as Method 5308.4.

In the test, liquid samples (lOOoca) are in the presence of

6.45 Metallee of each listed in Table cm (72 hours), heated to 32 ⁰ C. Air is passed through the sample at a rate of 5 l / Sΐα, blaeenwelee. The corrosion is measured as the weight loss per unit area dtr of surface.

BAD OFlJGJNAL

009832/1614

Table II

ο ο

composition Oil P Mg Corrosion, Cu mg / cm Ag increase Increase in Oil P + weight # 2.2'-
Dipyridylamine ■ - · '■ -19, «7 Al -Oo 13 Pe + Oo 07 the acid number viscosity Vo ο oil P + lWeight # Salt ¹¹ A "*! = 1.61 + Oc 02 -0.30 -26 ο 9 + Oo 14 17 oil. (37.8 ⁰ CJ, Io . 1 Oil P + .lweight # 2,2'- ^: ~~
Dipyrylamine +
OolGen ^ SaIa "A * +0.08 -1.55 +0.18 + Oo 14 8 "8 solid 2 + Oc 04 -D.13 +0.05 +0.27 38o9 15o8 3 +0.30 +0.17 0.1
'it ., 379 4th 9o9

B.!

O ί

r-

'Sals "A" is a mixed salt of monochloromethylphosphonic acid and a mixture ▼ 00 primary

cn co

CJl OO

Several inferences can be drawn from these results. The rather strong corrosion of copper, iron and / or magnesium is caused by the synthetic base oil alone without additives, or if it is either only the cyclic amine or only the salt ala contains additive. However, it includes both the salt as well as the oyolic amine, so will the corrosion all metals considerably reduced.

The results in Table II not only illustrate the excellent ones Corrosion-preventing properties of the additive mixture Clay SaIs and cyclisohem amine, but also the increased resistance against oxidation. The increase in acid number and the viscosity (all qualitative measures for the stability) 'considerably lower for the oil that the Sale and the oyolieoh contains lain than for the oil with no additive or only with tinea Part of the Suaatsfsmieobee.

The oils containing "a * StJts and Aas oyoüeohe AsIn and auoh dadurefc besoaders advantageous that they have an extremely low lead corrosion tiigt »* Synthetic Sohaitrile, the «Ytllsebe eel & t« la antioxidant deflead, In Abweeenfctit »Anti-corrosion agents, such as 2,6-di-tert.butyl-4-4iej * t hy laeino-p-o resol, generally corrosive to lead. SÜLti VlH much leiobttr attacked than other mullies, such as steel, , Magnesium, copper and silver, and lead niob! from the corrosive results of other metals will. Pen difference across the values for ÄeUt0rro # lon and for normal Xorrpslon soaps el «? Er

009132/1814

same as the results for Composition 3 in the following Table III with those of Composition 2 in Table II. The comparison shows that in a pentaerythritol ester oil 2.2 '»Dipyridylamine for most metals as a corrosion preventive Agent works, but it promotes lead corrosion.

The lead corrosion caused by the cyclic amines is essentially eliminated by the addition of the salt. This is shown in Table III below, which shows the results of the lead corrosion tests for the oil "F" (the pentaerythritol ^{ester base described in Table II) alone, for the oil 11} F "with an eye- * liechen amine as an antioxidant, and for the oil" F " with the salt and the cyclic amine.

The oils are subjected to the MacCoull Ryder test and the SOD bleaching test. The EacCoull-Byder test runs for 5 hours at 163 ⁰ C. Dieeer test is described in the individual SAS Journal £ 0, 8, p 336 (Aug. 1942). In the SOD Bleikorroeioneteat rapidly rotating · panels of lead and copper are erhitit in an oil sample for 1 hour at 163 ⁰ O, while air is blaaenweiaa duroh passed the test. Dieter Teat is in the federal Teat Method Standard Vr. 791a, procedure 5321.1 carried out. The marriages tested and the results obtained are given in Table IXI above.

009I32 / 1SU

Tatelle III

No. Composition MacCoull Hyder
Lead corrosion
Weight loss in g
(163 ⁰ C 5 St ₀ ) SOD lead
corroaion,
me / 6p45om2
Weight loss
(163 ⁰ C 1 pc.) 1
2
j5
4th
5 oil ρ ^x >'· ^!
oil F + l weight £ phenyl-alpha
naphtylamine
oil F ♦ lQfe * $ 2.2 »-
SipyrjLdyiamine
oil F + l Weight phenyl-alpha
naphthy-lamin + 0.26ew ^
SalE, ^M A ^M
oil F + lGewji 2.2 -
Dipyridylamine + 0.1Ge * ^
Salt "A * -O »0296
•
-2 "3174
-Io8285
-Ο »0025
-O * 0024 -o5.70
-5 »94
•
-Oo06 '95Geiij £ alifchatisolie C,. ^ Monocarboxylic acid ester clay
Pentaerythritol and SötiijG allphatieohe Cc ^ ₀ * -Mono>
oarboneäureeeter tod dipentaerythritol. M.
I.
■ · -J
■ -: v

8AD ORIGINAL

^ 09832 / 15U

Claims (1)

Claims Lubricant mixture, characterized in that it is a lubricating oil, an oyclisohes amine and a salt of an aliphatic Contains amine with at least 8 carbon atoms and an Üalogen-Οη ί-alkylphosphonic acid. 2. Sohmiermittelgemisoh according to claim 1, characterized by that it contains a synthetic lubricating oil as a lubricating oil. 3; Lubricant mixture according to Claim 2, characterized in that it contains an ester as the synthetic lubricating oil. 2o ~ ^{i 'arl> oic acid} contains _- Sohmiermittelgemisoh according to claim 3, characterized in that it alcohols A3 as a lubricating oil an ester of a C ^ _2o ~ and a 0,. 5. Sohmiermittelgemiflch according to claim 4, characterized daduroh., that as a lubricating oil it is an ester of a C ^^ 'alcohol and a C,., p-carboxylic acid. 6. Lubricant mixture according to claim 4-5, characterized by that the ester is derived from a mono- or polyhydric alcohol. 7. lubricant mixture according to claim 4-6, characterized in that that the ester of a single or female isohen derived from aliphatic carbonic acid. 009832/1514 Lubricant aggregate according to claim 7, characterized in that that more than one of the named eaters is used. 9. The lubricant mixture of claim 8, characterized in that it _s as a lubricating oil containing the Bisazelat of "2,2,4-trimethylpentanol ~ l and the Triheptanoat of 1,1,1-Irimethylolpropan. 10. Lubricant mixture according to claim 6, characterized in that that it is used as a lubricating oil aliphatic CV ,, - monocarboxylic acid ester des Pentaerythritε and aliphatic Ce ^ Q-Monocarboneäureeater of dipentaerythrite. 11. Schmie ^ medium mixture naoh claim 1 - 10, characterized in that that it contains 0.01-10 wt # of the cyclic amine. 12. Sohmiermittelgemisoh naoh claim 11, characterized in, that it contains 0.02-5% by weight of the oyolie-like amine. 13 «Soothing agent mixed with claims 1-12, characterized in that that the oyolieohe amine is an aromatic or heterooyclieohen The bed opens. Sonic agent mixture according to claim 13, characterized by that the olefinic amine has a benzene or naphthalene residue. Sohmieriaittelgemjßoh naoh Anopruch 14, daduroh labeled, that h1.h oyolifiichee amine diphenylamine is used,. BATH ORIGINAL 009832/1 $ U 16. Lubricant mixture according to claim 13 »characterized in that that phenyl-alpha-naphthatfcjlaiain is used as the cyolisohes amine will" 17ο 8ohmiermittelgemieoh according to Anepruoh 13 »characterized by that the cyclic amine has a pyridine or quinoline residue. 18. Sohraiermittelgemisoh according to claim 17, characterized in that » that all cyclic * amine 4-aminopyridine is used. 19 · Sehmiermittelgemiech according to claim 17 »thereby free of charge, that 2,2'-dipyridylanine is used as the oycliechea amine will. . 20. Lubricant mixture according to claim 13 »14 and 17» thereby marked »tafi more« le «ines of the named oyoliechen Amines is used. 21. ftohmlermittelgwmiaoh neon Anepruoh 20 »because you know it is worth the fact that it contains diphenylmoin and 2,2 ^I -dipyridylaain. 22. Sohaiermittelgemitoh according to Anepruoh 1-21, daduroh gtkenneelohnet, that "0.005 - 5 0 * ^ dt" Salsee holds. 23 Sohmiermitteigtndeoh NaOH Claim 22 »daduroh gekenneeiohnet that O Ol ₁ - 5 contains OEW ^ of the salt. 24. SohmioruiitUigömlecii naoh Anspruoh 1-23 »daduroh gekena« draws that the Qewiohtsvernaltnis des Seise "" un oyoli The amine is 0.03 / 1 to 10/1. -. '008S32 / tlU 25. Lubricant mixture according to claims 1-24, characterized in that the salt is derived from a primary or secondary C ₈ ^ q-alkylamine * 26 “Sobmiermittelgemiseh according to claim 25, characterized! that the salt is derived from a primary or secondary ^c i2-24. "" ^Al kylamine · 27. Lubricant mixture according to claim 25 -26 ₅ daäurch gekennzeioh * net i that the salt is derived from a primary or secondary alkyl amine with a tertiary AIk ^! Group. > 28ο SohmiermlttelgemiBoh according to claims 1-27, characterized in that that the salt is derived from more than one of the primary or secondary amines mentioned. 29 * Schmieraittelgeisoh according to claim 28, characterized in that the courtship is derived from primary Cj ^ gj-'fcert.Alkylaminen or from primary C ^ ₈ _ _e2 2 "'' ^fcel " ^{fc # A} ^^ y ^ ^amines . 30. SohmienaittelgemieciT according to claim 1 - 29, characterized in that the SiIz is derived from a halogen-C ^^^^^^ P ^ ⁰⁹ ? ^ ⁰¹³ "* acid. 31. Sohaiermittelgfmisoh according to claim 30, characterized by that sioh the salt of a mono- or Sihalogen-C ^^ g derived from phosphoric acid. BATH ORIGINAL 32o Sehmiermittelgemiech according to claim 31, characterized in, that the salt is derived from Monoohlorniethylphosphonsäure. 33 «lubricant mixture according to claim 31» characterized in that the salt of!, L-dichloroethylphosphonic acid
derived. 34 * Additional mixture for ei: i lubricating oil, characterized gekennzeiohnr ^ "dal n it a oycliBchee On ^ and a salt of aliphat- ^ß o ^KISSING
Amine with at least 8 carbon atoms and eiti-c halogen-C ^ j-Alkylphoephonsäiare contains "