DE1568247A1 - Process for the preparation of organometallic compounds of orthophosphoric acid esters and amine salts thereof - Google Patents

Description

Process for the production of organometallic compounds of orthophosphoric acid ethers and amine salts thereof

The invention relates to new organometallic compounds τοη Orthophosphoric acid esters »new amine salts of such compounds, hydrocarbon products containing the amine salts, and a new process for the production of the organometallic compounds. They new organometallic compounds of orthophosphoric acid esters are certain metal compounds of acidic hydrocarbon orthophosphates, and that Process for their preparation consists in the implementation of -a organic hydroxy compound with a halide of a polyvalent metal and phosphorus pentoxide.

Normally liquid raw hydrogen products such as fuels and lubricating oils contain additives to improve them

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Performance indicators. Additives are added to fuels such as gasoline in order to improve their various performance parameters improve, e.g. to help keep the carburetor clean, to counteract surface ignition and rust formation and to prevent the carburetor from icing up. Lubricants contain various additives, e.g. to improve your ViBOOsity index and its lubricity. You have accessories different potencies and often it is necessary to add several additives to a single product.

It has now been found that amine salts of certain metal compounds of acidic hydrocarbon orthophosphates have a beneficial effect by having a cleaning effect on the Exercise the carburetor and the intake system, prevent rust formation and carburetor icing, reduce the increase in the ootane number requirement and, in the case of liquid hydrocarbon fuels, counteract surface ignition Amine addition compounds are good soothing agents for addition to lubricating oils.

The new amine salts are neutralization products from * ■

and acidic hydrocarbon orthophosphates of a metal of Group IV B dos Periodic Table. Bas periodic table of the elements referred to here are in Handbook of Chemistry and Physics, 31st Edition, 1949

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Shown on page 336. The intermediate metal compounds of the acidic hydrogen orthophosphates correspond to the following general formula:

Formula I / "" (0H) (OR) 0P0-_7 _n M / "- 0PO (OR) ₂ J ^ ₁ ,

wherein M is a metal of group IV B, such as titanium, zirconium or Hafnium, η an integer from 1 to 4, n 'an integer from 0 to 3 means that the sum η * η * equals' the valence of the Metal M and each of the radicals R is a hydrocarbon group, e.g. one with 1 to about 30 carbon atoms, means. The metal M can be trivalent or tetravalent. M is preferably tetravalent titanium. From formula I. it can be seen that the metal compounds of the acidic hydrocarbon orthophosphates and their amine salts, which are here auoh as ammonium derivatives, additlons of amines or simply referred to as additives, can contain 1, 2, 3 or 4 acid groups (OH) per metal atom. Di «Qeeamtansfthl the carbon atoms can range from 4 to over 100 and is preferably in the range from about 4 to 60. Preferably, the intermediate metal compounds of the acidic hydrocarbon orthophosphates contain 2 or 4 Acid groups: they can be broken down by the following general Represent formulas:.

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(a) / "(0H) (OR) 0P0-_7 ₂ M /" - OPO (OR) ₂ J ₂ tod

(b) MZ ^- -O ¹ O (OR)

Herein, H means a hydrocarbon group with Ί to about 30 carbon atoms and M tetravalent titanium or zirconium.

The intermediate iron compounds of the formula I, ie the metal compounds of the acidic hydrocarbon orthophosphates, can, b · - before an acid group thereof is neutralized with an amine, by reacting a hydrocarbon dihydrogen orthophosphate of the general formula PO (OR) (OH) ₂ * in the E is a hydrocarbon radical, as in the formula I, or a mixture of a hydrocarbon dihydrogen orthophosphate and a di (hydrocarbon) donohyorthophosphate with a halide of a metal from group IY B of the periodic system in dispersion or I »öeuhg in an inorte organic solvents are produced · The di (hydrocarbon) monohydrogen orthophosphate corresponds to the general formula PO (OR) ₂ (OH). As will be explained in more detail below, these intermediate products can also be prepared by reacting a hydroxy compound, for example an alkanol, alkenol or phenol, with a halide of a metal from group IV B and phosphorus pentoxide. This allows direct synthesis of the intermediate products from the raw starting materials.

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Typical examples of halides τοπ metals of group Z? B of the periodic table are titanium trichloride, titanium tetrachloride, zirconium tetrachloride, zirconium triochloride, titanium tetrabromide, hafnium tetrachloride and the like. The reaction temperatures are preferably in the range from about 40 to 110 ° C., in particular from about 75 to 90 ° 0. Depending on whether the metal is in the trivalent or tetravalent state, about 3 or 4 moles of orthophosphoric acid per mole are old Halide implemented. The molar ratio of the reaction participants can, however, vary within wide limits; The tetrahalides can be reacted with a dihydrogen mono- (hydrocarbon) orthophosphate or with a mixture of a phosphoric acid monoester and a phosphoric acid diester in proportions of about 3 to 5 moles of orthophosphoric acid ester per mole of tetrahalogenide. The inert solvent used is preferably hydrocarbons, such as aliphatic or aromatic hydrocarbons. For example benaol, toluene, heptane, octane, hexane etc. the inert organic solvent does not have to be a hydrocarbon, but you can also use ether or halogenated hydrocarbons such as ethyl ether, tetrahydrofuran, carbon tetrachloride, chlorobenzene ucnr.

If a mixture of phosphoric acid with one and two acid groups per molecule is used in the reaction described above.

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is used, this mixture should preferably be at least 10 wt .- ^ and in particular at least 40 wt .- flt of WL hydrogen mono- (hydrocarbon) -orthophosphate _f since the monohydrogen-di- (hydrocarbon) orthophosphate If they are reacted with metal halides, they give compounds without free acid groups which cannot be neutralized with an Aain. The conversion of a dihydrogen ono (hydrocarbon) orthophosphate with titanium tetrachloride and a sitane tetra- / monohydrogen-mono-hydrocarbon) orthophosphate can be represented by the following equation

TiCl ₄ + 4 PO (OS) (OH) ₂ > Si / ΌΡΟ (ΟΗ) OHj ^ ₄ + 4 HCl,

in which B is a hydrocarbon radical having 1 to about 30 carbon atoms.

If you use the old metal halides Geaieohe for implementation from a dihydrogen mono- (hydrocarbon) orthophosphate and a »monohydrogen-di- (hydrocarbon) -orthophoephate, in this way one obtains mixtures of products in which some · Λ · γ Phosphate groups do not have four free hydroxyl groups, »end up having fewer than four acid groups, and part of the ·» B «action product also consists of compounds without acid groups, e.g. a titanium tetra- / d "i- (hydrocarbon) -orthophosphate7.

Except for the connections between Porael I and those "who do not"

contain free acid group, as they are when using the di-

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(hydrocarbon) orthophosphates as reaction participantsii can be obtained, the reaction often contains aieoh small amounts of other compounds, not all of which are known, including compounds in which both acid groups of one or more of the dihydrogen-mono (hydrocarbon) -orthophoephate are directly bound to the Hetallaton, e.g. compounds of the following general formula, in which one of the phosphate groups has two oxygen atoms is bound to a tetravalent metal:

(OR) ΟΡΟ- 7 «<> 0 (OR)

H herein, H denotes one of the metals indicated above and H denotes a carbon residue of 1 to about 30 carbon atoms. The mixture of compounds that is formed during the reaction can, however, also be neutralized with an amine without separating off the individual metal compounds or metal complex compounds and as an additive to fuels, such as gasoline, or to Soaking oil can be used. It is also not necessary, although generally in two dimensions, to be used during manufacture to separate the metal compounds formed from the amine salts from the solvent before use.

For the preparation of the addition compounds in the sense of the invention, all organic amines can be used, the AmIn-

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form salts, e.g. those with 1 to about 30 carbon atoms. The amine can be primary, secondary or tertiary, a aliphatic, aromatic or alicyolic amine be · Si · Oyolic amines can be carbooyolic or heterooyolic. The amine can be a mono-, Si, tri- or other polyaain be. The aliphatic as well as the aromatic and alioyollschen amines can be derived from unsubstituted hydrocarbons or from hydrocarbons have various substituents such as hydroxyl groups.

The following general formulas indicate preferred amines, which can be used according to the invention:

(a) R ² - H - R and (b) R ² - H- ¹

H
R ¹

H (CH ₂ J _n R ¹ RR ²

Here, R denotes a hydrocarbon radical, the radicals R

2 and R can be hydrogen atoms or hydrocarbon radicals η is an integer from 2 to about 10 and the total number of carbon atoms in each amine is 1 to about 30. Preferably, R is an aliphatic hydrocarbon radical and the radicals R ¹ and R ² are hydrogen atoms or aliphatic hydrocarbon radicals. The aliphatic hydrocarbon radical is preferably an alkyl or alkenyl radical, in particular one having 6 to about 24 carbon atoms.

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Typical examples of suitable amines to neutralize the metal compounds of the acidic hydrocarbon orthophosphates are methylamine, ethylamine, diethylamine, propylamine, tripropylamine, iBopropylamine, butylamine, ieobutylamine, hexylamine, 2-ethylhexylamine, ethylamine, dodeoylamine, 2-propyldecylamine, 2-propyldecylamine. Pentadeoylamine, tetradecylamine, octadecylamine, 6-butylootadecylamine, eicosaniine, e ^ -Dimethyl-S-propyldeoylafflizi, 8-hexyllO-isobutyloctadecylamine, diootylamine, tribensylamine, heradecylamine, 1-ethyl-oleylamine, linoleum-octylamine, hexyl-oleylamine, Nylodecylamine, hexyl-oleylamine, Nylodecylamine, hexyloylamine , 10-doamethylenediamine, xthylenedianine, 1,2-propylenediamine, 1,12-dodecamethylenedianjine, tetramethylenediamine, 1, 6-hexamethylenediamine, trietnylenetetraalive 1,2-phenylenediamine, benzylamine, 5,3'-biphenylenediamine, 3-biphenylthylamine, 1- , 1-pluorenamine, aniline, N-methylaniline, Ν, Ν-dimethylaniline, 2,3-phenylenediaain, 2-purenai3ine, piperaain, piperidine, purfurylamine, N-cyclohexylheptylamine and the like. You -amines can also have different sub-substituents on their Eohlenwaaserstoffreaten, such as hydroxyl groups »such as alkanolamines» e.g. diet nanoclamin, 3t3 ¹ * -hydroxydipropanolamine, isopropanolamine and the like ·

The hydrocarbon radical bound to the phosphate group can be aliphatic, aromatic or cycloaliphatic » SB · an alkyl, alkenyl, aryl, aralkyl, alkaryl radical, etc. The aliphatic group can be saturated or unsaturated» s «B ·

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contain unsaturated mono-, di- or polyolefin bonds The hydrocarbon group R in the formula I can also have various substituents, such as halogen atoms.

Typical Sihydrogen-oono- (hydrocarbon) -phosphates and monohydrogen-di- (hydrocarbon) -orthophosphates which can be used according to the invention are orthophosphoric acid monoootyl ester, orthophosphorus aaonolauryl ester, orthophophosphoric acid ethylanyl ester, orthophosphoric acid (orthophosphoric acid-tert.-butyl-orthophosphate, orthophosphoric acid-tert-butyl-orthophosphate, orthophosphoric acid-tert.-2-orthophosphate, orthophosphoric acid-tert-butyl-orthophosphate) Esters, orthophosphoric acid mono- (2-ethylhexyl) -ester, orthophosphoric acid-nono- (n-ootyl) -ester, orthophosphoric acid-aiono-isooctyl ester, orthophosphoric acid-isoamyl-isooctyl ester, orthophoephoreic acid-monononyl ester, orthophosphoric acid-ethyl-nonophosphonyl ester, orthophosphoric acid-dinophosphonyl ester oonocetyl ester. Orthophosphoric acid monotetradecyl ester, orthophosphoric acid nonostearyl ester, orthophosphoric acid diioosyl ester and orthophosphoric acid inonoeicosyl ester. Examples of unsaturated aliphatic Orthophosphorsäureester are, like orthophosphoric acid Bonooleyleeter, orthophosphoric acid dioleyl ester, Orthophosphorsäurs-dilinoleyl9ster, orthophosphoric acid oleyl-lauryl ester, Orthophosphoreäure-monolinoleylester, Orthophosphorsäureäthyl _r linole7lo8ter, OrthophoBphorsäure-mono-4-heptenyleeter, orthophosphoric acid rDono-ö-decenylester and »Typical phosphoric acid esters or aryl groups are phenyl, naph-

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thyXester and your substituted Bss-ivat ©? » wi® Qs

phosphoric acid ethyl benzyl ester phenyl ester, orthophosphoric acid monophenyl ester, orthophosphoric acid lauryl phenyl ester »orthophosphoreaure-dinaplitiiyleterf Orthophosphoric acid mononaphthylethers, orthophosphoric acid aonocresyl esters, orthophosphoric acid dicreeyl esters, orthophoephoric acid monoxylyl ethers, ortophosphoric acid mono-ethylplienyl esters and the like. Typical examples of phosphoric acid esters with cycloaliphatic groups are dicycloheptyl orthophosphoric acid, monooycloheptyl orthophosphoric acid Orthophosphoric acid di ~ (ethylcycloheptyl) ester »Orthophosphoric acid-BJonocyclopentyleeter and the like»

The amine salts can be prepared by simply neutralizing the free acid group or acid groups of the ketally bonds of the acidic carbonic orthophosphates. The formation of the addition compound can take place at room temperature; However, higher temperatures of about 36 ° O are preferred. Each of the acid groups of the acidic orthophosphoric acid ^{ester is preferably neutralized with a basic nitrogen atom 1 of} the amine, although this is not necessary. The neutralization can be carried out by simply adding the amine, the pH of the non-neutralized compounds being brought from less than about 5 to at least 6 or 7

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will. The neutralization can also be carried out by adding the stöohioieetrischen amount of amine to the respective Hetallyerbonds dee acidic hydrocarbon orthophosphate. Uses aan a mbnoamin, such as oleylamine, and neutralized e & mtlioh · Acid groups, amine addition compounds are obtained following general formula:

/ "(0H) - A (OR) 0P0_7 _n M /" ΌΡΟ (OR) _2- T _n

in which M is a metal from group IV B, R is a Kohlenwaaeerstoffrest with 1 to about 30 carbon atoms, A is an AnIn, η is an integer from 1 to 4 and n * is an integer from 0 bl * 3 and the sum η + η ^{1 is} equal to the valence of the metal M.

The new amine salts are suitable as additives to liquid hydrocarbon products, namely as lubricant additives, as corrosion retarders, anti-icing additives, detergents, additives against engine stalling and petrol additives to reduce the increase in the engine's oot number requirement. For these purposes, the hydrocarbon radical of the orthophosphoric ester should preferably be at least 6 Carbon atoms, e.g. containing 6 to 22 carbon atoms, and branched hydrocarbon groups such as the 2-ethylhexyl group or the 4-oxylphenyl group are particularly preferred. Psrnsr is intended to be preferred for these uses

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the amine also contain at least 6 carbon atoms, for example 6 to 24 carbon atoms, and in particular the amine should be an alkyl or alkenyl mono- or diamine. The amount of new amine salts in the various products can vary within a wide range and depends on the respective fuel or lubricating oil base to which the sale is added and on the intended use Weight jC vary. The hydrocarbon product can be produced by simply dissolving the amine salts in the hydrocarbons.

The new amine salts are particularly suitable as gasoline additives, as they give the fuels the properties indicated above. The gasoline can be leaded or unleaded . White tea gasoline is preferred. A preferred Ausfuhrungsfom the invention is therefore a Benzlngemisoh on the basis of one-* boiling in the gasoline range, gebleiten fuel containing about 0.001 to 0.05, preferably about 0.002 to .025 "in particular about 0.0025 to 0.02 part by weight 56 to the contains new amine salts. Besides gasoline, the amine salts even in small amounts to other hydrocarbon products, such as diesel oil "may be added to impart rust protection, etc." Under "petrol", "boiling in Bensinbereioh fuel on Kohlenv / asserstoffbasis" and similar expressions are counter oil

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to understand fractions that boil in the gasoline range (e.g. between about 10 and 232 ° C). The term "lead ^11" refers to a gasoline to which a small amount, for example between 0.027 and 1.585 ml per liter, of an organometallic compound that acts as an anti-knock agent, such as tetraethyl lead, tetraethyl lead, tetraisopropyl lead, etc., has been added .

Except for the new amine salts and possibly lead anti-knock agents can the gasoline e.g. still light hydrocarbons

Substance lubricating oils with Yiscosities of around 50 to 200 Saybolt seconds (SUS) at 37.8 ° C and viscosity indices between approx 30 and 120 in amounts between about 0.1 and 1.0 wt .- ^ included.

As additives to lubricating oils, the new amine salts improve this Interface lubrication sheets of the same. Lubricating oils that the contain new amine salts, prevent the alternate sliding and plague, as is often the case with automatic release coupling surfaces occurs.

In lubricants, the amount of amine salts can be within wide ranges, e.g., from 0.01 to 10% by weight, preferably from about 0.1 to 5 £ * aw .- * #, vary. For the production of lubricating oils can use a wide variety of mineral oils or synthetic oils or mixtures thereof can be used. Suitable mineral oils

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BB are the neutral oils of types 100 and 200, light and heavy medium mineral oils, bright stock oils and mixtures of such oils. As synthetic lubricating oils come z. B. diesters., Polyesters, silicones, silicic acid esters, fluorocarbon compounds, phosphoric acid esters and the like.

Typical amine salts which can be prepared according to the invention are titanium bis / ari- (2-ö; thylhexyl) -orthophoephat7-bis- ^ ono- ("coconut ¹¹ -aimaoniua) -mono- (2-ethylhexyl) -or.thophosphate ^ ⁷ , hafnium- tetra- ^ iono- (laurylamionium) -mono- (2-ethylhexyl) -orthophosphate7 »zirconium-te t ra- ^ ono- {laurylammonium) -mono- (2-ethylhexyl) -orthophosphate /, zirconium-tetra- ^ Dono ~ (oleylammonium) -mono- (2-ethylhexyl) -orthophosphate7, zirconium-tetra- ^ nono- (propylejDmonium) -mono- (4-octylphenyl) -orthophosphate7, the addition product of N-oleyl-i ^ -propylenediamine and zirconium bis - / d "i- (2-ethylhexyl) orthophosphate7-blB- _/ ^ 5ionohydrogen-mono- ^? - ethylhexyl) orthophosphate7, the addition product of hexamethylenediamine and titanium-tetra- ^ donohydrogen-mono- (8-ph« nylootyl ) -orthophoephatjr the addition product of ethylenediamine and titanium bis ~ / d * i- (isobutyl) -orthophOBphat7-bis- ^ ionohydrogenmono- (i8obutyl) -orthophob.o8phat7, titanium (IV) - / mono- (laurylammonium) -mono - (2-ethylhexyl; -orthophosph.ai ^ ^ir -tri- / Ii- (2-ethylhexyl) - orthophosphate7 _? Titan-bis- / 5i- (2-äth.ylhexyl) -orthophoephat7 « - ( oj.oyleinmoniuni) -mono- (2-äthylhaxyl) -

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- (2-ethylhexyl) -o

ammonium) -mono- (2-ethylhexyl) -orthophoephat /, Ti tan-bie- ^ Ti- (2-ethylhexyl) -orthophoephat7-bie- ^ Bono- (etearylamnoniua! no- (2-ethylhexyl) -orthophoepha ^, titanium -tri - ^? ono- (dioctyli moniuo) -nono- (4-octylphenyl) -orthophoephat7- / Ti- (4-ootylphenyl) -orthophosphaJj7, titanium-tetra- ^ 5bno- (oleylamnoniuo) - «o ~ no- ( 2-ethylhexyl) -orthophoephat /, titanium-tetra- ^ ono- (4-ieopropylcyclohexylammonium) -mono- (2-ethylhexyl) -ortbophoephaj7 »Ti tan-tetra- ^ ono- (oleylammoniun) -nono- (oleyl J-orthophoaphaj ^ »Titan- te tra- ^ iono- (ben zyl ammonium) -mono- (eicoeyl) -orthopho · - pna ^ 7, titanium-tetra- ^ iäono- (benaylannBoniun) -aono- (2,4-diethyl-4 -äthylheptyl) -orthophoepha ^ 7 _t titanium-tetra- ^ ono- (oleylaaeonium) -mono- (cycloheptyl) -orthophoephaJj7 _r Ti tan (III) - tri - ^ / iono- (laurylammonium) -mono- (2-ethylhexyl) -orthophosphai7t zirconium (III) -tri- ^ ono-ioleylammonium) -mono- (2-ethylhexyl) -orthophoBphat7, the addition product of triethylenediamine and titanium tetra- ^ nonohydrogen-mono- (cetyl) -rorthophoephat7, titanium (IY ) -tri- ^ ono- (decylammonium) -mono- (naph thy 1) -orthophoepha ^ -iiono- ^ Ji- (naphthyl) -orthophoepha ^ 7, HainiuiB-tri- ^ iono- (oleylaiaionium) -mono- (benzyl) -orthophoephat7, Titanium (IV) ^^ röno- (palaitylamroonium) -mono ~ (linoleyl) -orthophoephaJ ^ ⁷ -tri- _i / Ti (linoleyl) -orthophosphate7, the addition product of fiperasine and H * fnium- ^ onohydrogen-mono- (4 -isopropylphenyl) -orthophoaphat7 ^, the addition product of diethanolamine and titanium tri- ^ ono-

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hydrogen-mono- (3 »4-dipropyleicosyl) -orthophbsphatj7f the addition product of aniline to titanium-tetra-Zmonohydrogen-niono · (oleyl) -orthophoBphat7 ^r _i the addition product of 1,4- phenylenediamine to titanium-bia- ^ monohydrogen- niono- (3-iBopropyloyolohe3qrl) -orthophoaphai ^ 7-bis- / d "i- (3-iBopropyloyclohexyl) -orthophoephatj7 ..

example 1

200 g of a mixture of 71.7% by weight of orthophoephoreic acid-2-ethylhexyl ester and 28.3 % by weight of orthophoephoreate-di-2-ethylhexyl ester are placed in a solution of 23.6 ml of titanium tetrachloride in 250% within 15 minutes ml of heptane infused. The mixture is heated to 93 ° C. while stirring and passing in air to drive out the hydrogen chloride. Mused, the Gfeiqiech held for 4 hours at 93 ° C and stirred overnight under a slow bubbling of air through the löeung. The next morning the air flow is increased and passed through the solution for another half an hour. The heptane is driven off in a vacuum. The product obtained is a mixture of different titanium compounds with 4 moles of phoephate groups j · KoI titanium, such as the following compounds, in which the Reet CgH-Jr ₅ . a 2-ethylhezyl group means:

(a) 0!
- (b) Ti

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(ο) Z ~ (0H) (OC ₈ H ₁₇ ) OPOj ^ ₂ M.

(4) Z ~ (0H) (OG ₈ H ₁₇ ) OPOj ^ Ti ^ fOPO (CgH ₁₇ J (e), / "(OH) (0C ₈ H ₁₇ ) 0P0j7 ₃ Ti

Example 2

100 g of the product mixture obtained according to Example 1 are used neutralized with 1O7 »5 g of technical oleylamine in 69 g of toluene by simply mixing the constituents at 38 ° C. to form a salt. The salt is soluble in toluene. Another 100 g of the The mixture obtained in Example 1 is neutralized "it 01eyl-T" 3-propylenediamine in 54 "7 g of toluene. This aain salt is also soluble in toluene.

example 3

If, in the process of Example 1, the titanium tetrachloride is replaced by an equivalent amount of zirconium tetrachloride, the corresponding zirconium tetrachloride is obtained .B. 2irKonium ~ te tra- ^ Eonohydrogen-mono- (2-ethylhexyl) -orthophosphate7, zirconium-tri ~ / ionohydrogen-mono- (2-ethylhexyl) -ortho-PhOBPhEtZ-KOnO- ^ i- (2-Ethhyihexyl) ~ orthophosphaj ^ ¹ ', zirconium bis - ^ / di- (2-äthylhexylJ'Orthophospha ^ -bie- ^ bnohydrogen-aono- (2-ethylhexyl) -orthopboephaj ^ and the like. The amine salts of these zirconia fungi are obtained by simply

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the titanium reaction products used in Example 2 replaced by equivalent amounts of the mixed reaction products of zirconium described above *

Example 4

Using the procedure of Example 1 instead of Phosphoric acid 2-ethylhexyl ester Phosphoric acid ester with others Hydrocarbons, e.g. the n-dodecyl, phenyl, beneyl, 3-Butyl te trade csyl or 4-octylphenyl ester, the corresponding titanium compounds with the hydrocarbon groups specified above, which then continue with various Amines, such as oleylamine, can be converted to amine salts

Example 5

A mixture of 445 g of orthophosphoric acid mono-2-ethylhexyl ester and 55 g of orthophosphoric acid di-2-ethylheacyl ester is used from the drip funnel to a solution within 17 minutes of 63 ml of titanium tetrachloride in 500 ml of heptane was added. After 8 minutes, an orange gel has formed. After adding the entire phosphoric acid ester, the genic is under Passing heated nitrogen through it to generate the hydrogen chloride to drift out of the solution - after 45 minutes the gel has calibrated completely resolved. The mixture is heated to reflux temperature for a further 3 hours and the solution is then left to stand overnight. On that

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the solution is reheated and it becomes nitrogen for 2 hours Hindu guided. The main product of the reaction is titanium-tetra- / ftonohydrogen-mono- (2-ethylhexyl) -orthophoepha37, and small amounts of a similar product have also formed in which some of the phosphate groups contain two mono- (2-ethylhexyl) groups. You solution is then with technical Neutralizes oleylamine. The neutralization point is through Titrate a sample dissolved in ASTM gasoline to the sun end point determined against p-nitrophenol in methanol.

Example 6

A mixture of 8.25 g of orthophosphoric acid-dl-2-ethyl-ethyl-ester and 66.75 g of orthophosphoric acid-mono-2-ethylhexyl-ester is dissolved in 100 ml of heptane and the solution from the dropping funnel to a solution of 9.45 ml of titanium tetrachloride in 100 ml of heptane added. During the first half hour of the addition, it forms an orange oil, and so does the Most of the hydrogen chloride is formed during this time. When adding more phosphoric acid ester, the gel goes into Solution. After heating to reflux temperature for 15 minutes, nitrogen is bubbled through the solution and heating continued on the reflux condenser for a further 2 1/2 hours. The heating is then interrupted and nitrogen is continued for 30 minutes passed the mixture. The mix of heaktions that predominantly consists of Titan-te tra - ^ / mono- (2-ethylhexyl) -monohydrogen-orthophosphate 7

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is made with oleylamine using p-nitrophenol neutralized as an indicator of the Aminealz.

Example 7

50 g of a mixture of 89 * 5% by weight of orthophosphoric acid nono-2-ethylhexyl ester and 10.5% by weight of orthophosphoric acid fli-2-ethylhexyl ester are dissolved in 100 ml of anhydrous heptane. 9.4 ml of titanium tetrachloride are added to dry heptane,

and the solution is heated to dryness with stirring Phosphoric acid ester solution added. The whole is heated to reflux temperature for 1 1/2 hours while nitrogen is passed through. The solution is then left to stand overnight and then heated to reflux * temperature for 4 hours After cooling, the solution is poured into a 250 nl Measuring cylinder transferred. The product obtained is a mixture of clay Titanium tra- ^ onohydrogen-mon © * - (2-ethylhexyl) -orthophosphate7 This product is neutralized with diethanolamine to a water-soluble salt, the main component of which is titanium tetra- ^ dono- (diethanolammonium) -nono- (2-ethylhexyl) orthophosphate7

Example 8

80.5 g of a mixture of 89 wt .- ^ orthophosphoric acid mono-2-ethylhexyl ester and 11 wt .- ^ orthophoephoreic acid di-2-ethylhexyl ether are dissolved in 100 al of heptane and added with stirring a solution of 10.4 nl titanium tetrachloride in 100 al heptane

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added. The solution is heated to reflux temperature for three and a half hours while nitrogen is being passed through in order to drive off the hydrogen chloride. The? Ltan- ^ nonohydrogenaono- (2-ethylheyl) -orthophosphate7 _{4 obtained in this way} is neutralized with 70.1 g of "coconut" amine and the solvent is evaporated off in vacuo. The product is an amber colored liquid with a slight cloudiness. The yield is 153 * 8 g.

Example 9

A solution of 44.5 g of orthophosphorous acid mono-2-ethyl ether and 5.5 g of orthophosphorous acid di-2-ethyl ether in 100 ml of isooctane is added to a solution of 6.3 ml of titanium tetrachloride in 75 ml of isooctane. The solution is heated to reflux temperature for 3.5 hours while nitrogen is being passed through in order to drive off the hydrogen chloride. The solution contains a mixture of Titen-tetra- ^ aonohydrogen-mono- (2-ethylhexyl) ~ orthoph08phat7 with other titanium orthophosphateoa, which contain both 2-ethylhezyl groups and acid groups. This solution is added with 34.2 g of oil-1,3-propylenediamine neutralized the amine salts of the mixed titanium orthophosphates. The product is obtained by distilling off the solvent under reduced pressure.

- 22 -

A 54 058

Example 10

A mixture of 44.5 g of orthophosphoric acid Huo & o ^ -äthylhexyl «» ester and 5.5 g of 0rtäiophoephorsäiire ~ di-2 ~ ethylhexyl ester dissolved in 100 ml of Ieooctane and the solution to a solution of 6.3 al (10.87 g) titanium tetrachloride in 60 ml isooctane added. Large amounts of hydrogen chloride develop, and a solid material forms, which goes back into solution in the solvent. This solution is heated to reflux temperature for 3.5 hours while nitrogen is passed through the oven, until only a trace of hydrogen chloride can be detected in the gas stream with litmus. The solution contains a mixture of titanium phosphates with a substantial amount of titanium 6tra ~ ^ donohydrogen-iono- (2-ethylhezyl) orthophosphate7 and a smaller amount of titanium-bis- / Ii- (2-ethylhexyl) -orthophoephat ^ -bis- ^ ono-C 2-ethylhexyl) -monohydrogen-orthophosphaJ ^. 51.2 g of di-2-ethylhoxylamine are added to the reaction mixture. The isooctane solution of the amine salt of the acidic titanium hydrocarbon phosphate is washed with water, whereupon the isooctane is driven off in vacuo. The product is a clear, yellow, viscous liquid.

Example 11

Following the procedure of Example 10, 40.5 g of technical Tetradeoylamine added to the reaction mixture, and the solution

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A 54 058

The solution is washed twice with hot Salawaeser and filtered dry and the iaooctane is driven off in a vacuum. The product iet a clear, almost colorless, liquid. The spoil is 92.5 g.

Example 12

100 ml of heptane are cooled and with 6.28 al (10.86 g) üiitraitetrachlorid horrified. To the solution of the titanium tetrachloride 50 g of a cooled mixture of 89 wt .-? 6 Ortfc.ophosphoreäure-raono-2-ethylhexyl ester and 11% by weight of di-2-ethylhexyl orthophoephoric acid added in 50 ml of heptane. The Beeher glass, from which the phosphoric acid esters are added, is rinsed with another 50 al of heptane. The solution is heated to reflux temperature for 4 hours. The predominant one individual component of the heated to reflux temperature Product is.Titanium tetra- ^ monohydrogen-mono- (2-ethylhexyl) -orthophosphajj7. 58.5 g of oleylamine are added to the mixture and the heptane is driven off in vacuo. As a product you get a clear, yellow, viscous liquid. The predominantly single component of the product is the olaylamine salt of titanium tetra- ^ onohydrogsn-tnono- (2-ethylhexyl) - ^ rt? iophosphate 7.

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A 54 058 ♦ *

Example 13

25176 g of a mixture of phosphoric acid esters, which 14-β Orthophoephoreic acid-jaono-2-ethylhexyl ester and 11.33 g orthophoephoric acid-di-2-ethylhexyl ester are added with 25 ml Heptane mixed, and the mixture becomes a solution of 3 »794 β (2f2 ml) titanium tetrachloride in 50 ml heptane was added. The mixture is for 3 hours while bubbling through. nitrogen heated to reflux temperature. After evaporation of the solvent in vacuo, a white gelatinous color is obtained Hasse «This is neutralized with a solution of 18.5 g of di-2-ethylhexylamine in fentan and washed three times with water. The product is dried and the pentane is driven off.

Example 14

84 »0 g" orthophoephoric acid mono-2-ethylhexyl ester are in Dissolve 200 ml of toluene, and the solution becomes a solution of

«19 g of titanium tetrachloride in 150 ml of toluene added« Bas mixture is heated to Rüokfluastenperatur for 4 hours while passing nitrogen through. The product in the reaction mixture is iitan-tetra- / 9 ° no- (^^

phat7 A part of the reaction mixture which contains 8.8 g of the product can be neutralized with 2.5 g of oleylamine to form titanium tetra- ^ öono- (oleylammonium) mono- (2-ethylhexyl) phosphate7 be «The same procedure can be used for the corresponding

- 25 -909841/1625

A 54 058. if

Amine salts are produced if, instead of the oleylamine, equivalent amounts of isopropylamine, aniline, H-methyloyelohexylamine, isopropanolamine, 6-hydroxyhexylanine or 12-hydroxydodecylamine are used ..

Example 15

According to the example 14 for the production of titanium tetra- ^ njonohydrogen-mono- {2-ethylhexyl) -orthophoepha1j7 described Procedures can be titanium-tetra- ^ / mono- (decyl) -raonohydrogenorthophosphat7, titanium-tetra- ^ iono- (3-butyldodecyl) -monohydrogen-orthophospha ^, titanium-tetra- ^ / mono-i phenyl) -monohydrogenorthophosphat7 and titanium -tetra- ^ cnono- (4-octylphenyl) -aonohydrogen-orthophosphajb7 produce by replacing the Mono-2-ethylhexyl orthophoreic acid, 8 equivalent amounts of phosphoric acid monodecyl ester, mono-3-butyl dodecyl orthophosphoric acid, monophenyl orthophosphoric acid ester or orthophosphoric acid-aiono-4-octylphenyl ester is used.

Example 16 -

A solution of 15.3 g üütantriohlorid in 100 nl benzene is mixed with a solution of 63 g of orthophosphoric aono-2-äthylhoxylester in 150 ml of benzene. When the mixture is heated to 80 ° C, a solution is formed which contains titanium tri- ^ ono- (2-ethylhexyl) monohydrogen orthophosphate7

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A $ 4,058

1588247

tr

The compound dissolved in the reaction mixture is mixed with 30 g Heac ^ X amine neutralized to titaii-tri- ^ onot.

Example 17

This example reports on the basis of Table I tests for anti-icing protection in a carburetor engine through use of petrol containing the additives according to the invention " Sin single cylinder engine is with constant. Speed allowed to run, the conditions with regard to the intake air are adjusted so that the carburetor icing is favored. The test conditions are chosen so that when using the fuel base without the addition, the vacuum in the suction line rises to 63 Bg within 20 minutes. The engine is equipped with a carburetor throttle body made of glass or clear plastic, so that the icing up can be confirmed by inspection. As a fuel base a mixture of equal roughness parts isoootane and white spirit is used. The protection against icing is determined, meanwhile the increase the running time is determined, the use of a gasoline containing the Aain salt according to the invention in comparison To use a gasoline without such an additive, it is necessary to reduce the vacuum in the suction line to 63 na Hg to let rise. The results of these experiments, in which the vacuum required to reach the specified vacuum

- 27 -90984'f / $ 1 25

A 54 058 **

is referred to as "exposure time" can be found in Table I * Herein addition A denotes titanium tetra- / bono- (oleylaneoiiiun) -onM2-ethylhexyl) -orthophoephate7, addition B iet da leutra- ^ ieationsproduct of titanium -tetra- ^ onohydrogen- »onor, (? - ethylhexyl) -orttiophoepliat7 and H-oleyl -"! ^ - propylenediamine, while additive C titanium tetra- / iono- (laiLrylanmioniuia) -Bono- (2-äthylhexyl) -orthophoephat7 means·

Tabel : E * 101 Protection booster additive to gasoline 100 Zueata Percentage improvement in
Additional concentration, the exposure time, rergliohen
Gew · -Φ ait fuel base 97 A. 0.005 101 A. 0.005 62 A. 0.005 105 A. 0.003 99 A. 0.001 9β B. 0 _f 005 104 B. 0.005 59 B. 0.005 130 B. 0.003 B. 0.001 C. 0.005

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9098U / 1S2 5

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Example 18

This example shows with reference to Table II that the gasoline containing the amine salts according to the invention contribute to keeping the gasifier clean. A single-cylinder engine, which has been rebuilt in such a way that the amount of blowing past the piston rings is greatly increased, is slowed to run for 20 hours in a partially throttled state at constant speed for each attempt. The engine is equipped with a return line that returns the gases blown past the piston rings from the bumper cover to the air intake side of the carburetor. After a spring test, the carburetor is dismantled and assessed visually by examining the top and bottom of the throttle valve and the top and bottom of the venturi. The gasolines used in the experiments (with the exception of the fuel base, which does not contain any additive) contain the additive according to the invention in a concentration of 0.005% by weight. Have in Table II in the column "composition" specified letters have the following meanings: additive A is dae neutralization product of titanium tetrß- ^ onohydrogen-mono- {2-ethylhexyl) -orthophosphatj and Mleyl-1, 5-propylenediamine _f ·! Addition B let titanium tetra- '/ jaono- (oleylaWHsonium) ~ mono- (2-ethylhexyl) orthophosphate /; Addition C let Xitan-tetra- ^ ono- (laurylejmoniue) - »ono- (2 _T ättiylhexyl) -o? -Tho {jhoaphajt7; Addition D is the itutrm-

* -. BATH

90914171625

A 54 058

ionization product of titanium-tetra- ^ onohydrogen-nono -! - (2-ethylhexyl) -orthophoaphat7 and a mixture of primary ver «Weighted chain alkyls with 12 to 14 carbon atoms. The results of these tests can be found in Table II, where the quality rating 10 means complete purity and the quality rating 0 means strong black deposits.

T a b β 1 1 e II Reinhaitun «des Carburetor. Application Quality assessment Percentage improvement
in comparison to the driving
fabric base Fuel base 3.8 A. 7.4 95 A. 8.5 124 B. 6.4 69 B. 6.3 66 B. 8.4 121 C. 8.2 116 D. 6.0 58 example

Using Table III, this example shows that a gasoline (Fuel base), which is an amine salt according to the invention contains, the purity of the intake system in the event of burns. In the purity »test, a linear cylinder

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■ οtor »which iat so modified that the blowing past the piston rings is significantly increased» alternately §0 seconds without load la idle and 250 seconds with wide open throttle at 1050 rpm * 150 hours run. The motor 1st equipped with a Rüokführleitüng _t the vorbeigeblaeenen the piston rings gases from Stossstangendeokel to Luftaneaugloitung the carburetor zurtiokleitet · ffaoh each test is disassembled the intake system and with respect to visually the purity of the * carburetor _f the suction line and the area of the intake valve evaluated. The results of such a series of tests can be found in Table III. In the tests carried out with the additives according to the invention, the fuel base contains the additive in a concentration of 0.005% by weight. Additive A is titanium tetra- ^ ono- (oleylammonium) mono- (2-ethylhexyl) orthophosphate. Additive B is titanium tetra- ^ ono- (laurylammoniua) - ■ ono- (2-ethylhexyl)> orthophospha _a t7; Additive C is the neutralization product from. Titanium tetra- ^ onohydrogen-mono- (2-ethylhexyl) -orthophoaphaij7 and a mixture of primary branched-chain alkylaoins having 12 to 14 carbon atoms.

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Table III Purity dee anaaugayetena

composition Quality assessment
(completely pure
β 100) 20th Fuel base 36 A. 70 B. 75 C. 72 C. 68 example

Percentage improvement

in comparison to the driving

fabric beaie

94 108 100

This example shows on the basis of table Vf ₉ that the gasoline additives used according to the invention reduce the surface ignition in carburettor engines Hours at 1000 rpm, alternating 50 seconds with the throttle in the idle position and 250 seconds with the throttle wide open. The bitter hourly surface ignition count for at least «4 hours is compared with the count for the fuel base for each additional gasoline and reported as a percentage reduction. As an additive, titanium tra- ^ inono- {oleylammonium) -mono- (2-ethylheocyl) -orthophocphaj7 is used in these associations. The results can be found in the following table.

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909841/1625

A 54 058 T a , 005 belle IV oppression • 013 the surface guideline Additional concentration
in the fuel base, , 0365 Percentage reduction in
Surface ignition, cf.
chen with fuel base O ₁ i e 1 21 14th 0, 30th 0, 49 B β i s ρ

This example, in conjunction with Table V, the reduction in the increase of the octane requirement of a base fuel (gasoline), which contains an additive according to the invention "old base fuel without additive. A V-8-person motor vehicles ~) gate, which is converted so that an increased blow-by occurs on the piston rings will, or by using the pure Ireibstoffbasis * of the provided with the additional fuel erfihdungegemässen base in each experiment
125 hours alternating 50 seconds without load in idle and 250 seconds with medium load in medium
Speed run. The engine is equipped with a return line that guides the gases blown past the piston rings from the rocker arm cover to the air cleaner. During the test, which lasted 125 hours
the octane requirement of the engine with the throttle wide open at 1000 rpm, determined every 24 hours. The octane need will

■ A 54 058

plotted in the diagram in hours as a function of the duration of the experiment. The increase in the octane requirement is calculated in each case from the difference read off the curve between the octane requirement after a 100-hour period and the initial octane requirement. The results of such a series of tests are shown in Table Y; the additives are used in the propellant in a concentration of 0.005 wt. Additive A is titanium-tetra- 2? Äono- {oleylamzDonium) -mono- ( 2-ethylhexyl) -orthophoapni. ^ J Additive B is the neutralization product of titanium-tetra ^ / ^ mono hydrogen-mono- { 2-ethylhexyl) -orthophoephai7 and N-oleyl-1 » 3- propylenediamine} additive 0 is the neutralization product of titanium-te tra- ^ onohydrogen-iaono- ( 2-äthyöhexyl) -orthophoepha ^ and mixed primary branched-chain alkylamines with 12 to H carbon atoms.

0? abe 1 le V

Decrease in the rise ootane number requirement B.

Percentage reduction in the increase in the ootane number requirement compared to the addition with the fuel base

A 58

B 53

C 51

- 34 -9 Q 9 * £ 1/162

- -Ζ- '; ■ ■■■ 1SSS247

A 54 058 $ *

Example 22

A petrol mixture which al® Iorrosionir ^ asestSgpre ^ wiri ¹ ^ tarn Carburetor against di® Äasaumiliiag v © a A ^ lagertmges,

Ο *, rflächenEÜndui- ^ suppressed and iie ver sugert »is obtained by dissolving Sitan-tetra- ^ ono-Coleyl aOBoniun) -iDono- (2-ethylhexyl) -orthophoBphat7 in gasoline In a concentration of 0.04 g / l

Example 25

Another suitable fuel mixture consists of one Gasoline »which titanium tetra- ^ iono- (laurylamooniun) -aono- (2-ethylhexyl) orthophosphate7 in a concentration of Contains 0.01 wt. It.

Example 24

Another suitable fuel mixture is to dissolve Titan-bis- / d "i- (2-ethylhexyl) -orthophospha ^ -bis-2? Oao- (oleylaaooniun) -nono- (2-ethylhexyl) -> orthophospha ^ in gasoline in a concentration of 0.08 g / l.

Example 25 A suitable cooking oil mixture can be prepared by adding ^%

one Titan-bie-j / cTi- (2-ethylhexyl) -orthophospha ^ -bis- ^ ono- ^ (oleylamooniuin) -mono- (2-äthylhexyl J-orthophoaphaj ^ ίΛ! Teutral-

- 35 -909841/1825

A 54 058 Ji

Oil 200 dissolves in a concentration of 10 g / l.

Be i β ρ i e 1 26

A suitable lubricating oil can be produced indea »an Titan-te tra - ^ / mono- (lauryl ammonium) -mono- (2-ethylhexyl) -orthophosphate7 in mineral schnijröl in a concentration of ron 8 g / l dissolves »

Example 27

Ii tan-bie- / 3fi- (2-ethylhexyl) -orthophoaphaJ ^ -bie- ^ nonohydrogen- Bono «(2-ethylhexyl) orthophosphate7 is duroh implementation of 2 moles of phosphorus pentoxide and 1 mole of titanium tetrachloride old 6 hol 2- ethylhexanol-1 obtained according to the following equation)

P ₂ O ₅ + TiCl ₄ + 6

H ₅ O ₂

NmCH ₂ OH /

(RO)

₂ if

Ti

V *

(AWAY

+ 4 HOl

R here denotes the 2-ethylhexyl radical.

A reaction vessel equipped with an aeohanic stirrer, one Equal-pressure addition triohiter, thermometer, gas inlet tube and a reflux condenser protected by a Trooken tube is provided with a stopper, 400 ml of anhydrous n-heptane and 71.0 g (0.5 mol) of phosphorus pentoxide are added

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1563247

J!

sends. While stirring at such a speed that a uniform distribution is achieved, 47t4 8 (0 »25 Hol) titanium tetrachloride are then added. Finally, the 215 g (1.65 Hol) of 2-ethylhexanol-1 contained in the pressure equalization addition triofeter are allowed to flow into the reaction vessel at such a rate that the temperature of the reactants does not rise above 60 ° C. The solution is now a homogeneous developed. The. Eeaktioneteilnehmer are then heated to 98 Ibis 103 ° 0, and has soon subsided, hydrochloric development "wiuä dry air © torch passed the solution to tes acid gas faster zn ¥ Erfei» g © ii and beeelileimigen the reaction shown below. Once nit 'help of the Congo "red indicator no further Chlorwas-serstoffentwiokl can ^ mg festgestallt are going to" the n-Heptaa mmd the nloht raigesetzte "octanol vacuum ahdestilliert · You - distillation Ibis au a iiamperatur you 175 ° 0 an EsKldrusk of 25 Wt Hg. 275 g of a very blue-yellow syrup-like product are obtained in a yield of $ 99.

9Ο984Τ / 162

A 54 058

!8th

From the formula

calculated molecular weight 1109 »15

Calculated: titanium, wt. - ^ ' 4.32

Phosphorus, wt »-5 <>" 11 »17

Found: titanium, wt .- ^ 4.37; 4.30

Phosphorus, wt .- ^. 11.24t 11 t 15

pn

Refractive index n £ 1.4750

Density d ₂₀ 1.0836

Viseoaity, SUS up to 37.8 ° C 10 804

at 98.9 C 665 »6

Color according to AS2M 1/2

As already mentioned, the organometallic orthophosphates including those described above can all be produced by unsetung an acidic orthophosphoric acid ester with a halide of a polyvalent Met . They la commercially available acidic orthophosphoric acid esters are in general mixtures of orthophosphoric acid mono- and diesters in varying proportions, which often also contain free phosphoric acid as an impurity. From these commercially available orthophosphoric acid esters, organometallic before orthophosphates of reproducible composition can therefore be produced with difficulty. Often it is also necessary that ale impurity in the esters of free phosphoric acid contained prior to reaction with the halide dee polyhydric Metallee su remove.

- 38 098V1 / 1S25

ύΒ ^ ^ * ¹ ^ ^ fI / ** Τ

I 56824 /

JS

A 54 058

Bs has now been found »that is @ tall® ^ ganis3ht can also be prepared by reacting a hydroxy compound with a halide of a certain metal and phosphorus pentoxyä la an inert organic solvent. This implementation is done by simple Mixing the reactants at a temperature of about 10 to 120 ° C. During the reaction, the halide groups of the metal are displaced to form a metal salt with at least two orthophosphate groups, while the monovalent organic hydroxy compound has one or more hetero groups with each of the orthophosphate groups bonded to the metal forms. Except for the formation of pus and the bond to the metal can be one or more of the phoephate groups as well Acid group included. Hydrogen halide is formed as a by-product of the reaction.

In the direct production of the organometallic orthophosphates from the raw materials, the use of acidic Orthophosphoric acid ethers avoided as intermediates. This manufacturing method makes the process less expensive and enables the production of a wide variety of different organometallic orthophosphates.

The following general equations explain typical implementations within the meaning of the invention, where R is a hydrocarbon

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Substance group ait 1 tie about 30 carbon atoms, X a halogen atom and M a polyvalent metal:

.OR

+ 3 ROH + MX ₂

2 P ₂ O ₅ + 6 ROH + P ₂ O ₅ + 3 ROH +

1 1 /

(RO-J ₂ POMOP ^ + 2 HX

OH

(R0-) ₂ P-0- M

(R0-) ₂ P -O-MT ^ - OR + 3 HX

-o-p /

OR

As you can see, M in equation I is a two-valued metal »in equation II a yier-valued metal and in equation III a trivalent metal. The aetallorganisohen Orthophoephate seeds Oleiohung I as metal (II) - / STi- (hydrocarbon) -orthophoephatZ- ^ oonohydrogen-inono- (kohlenwaeser atof f) -orthophosphate7, those according to equation II as metal (IV) -Ms- ^ Ti- (hydrocarbon) -orthophosphate7-bie- ^ onohydrogen-aono- (hydrocarbon) -orthophosphate7 and those geaä ·· Equation III as metal (III) - / Ti (hydrocarbon) -ortno-

- (hydrocarbon) -orthophosphate7 be »ei without t.

The polyvalent metal halide used in the process according to the invention corresponds in the broadest sense to the general formula R ' _n , MX _n , in which R' is a hydrocarbon group with 1 to about 20 carbon atoms, n 'is a whole number

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from 0 to 2, M a polyvalent metal, X a halogen and η an integer of at least 2, such as 2 to 4 or 6 »and the sum η + n 'is equal to the valence of the metal M is. The halide of the polyvalent metal preferably corresponds to the general formula MX _n , where M is a metal with a valence of 2 to 4, X is a halogen atom and η is an integer corresponding to the valency of the metal, ie 2 to 4. The metal can, for example, be a metal from Group II, Group IV, Group VI or Group VIII of the Periodic Table of the Elements * The periodic table to which this definition relates can be found in "Handbook of Chemistry and Physios ¹¹ , 2 9th edition, 1945, pages 312-313. Preferably, according to the invention, the tetravalent metals of Group IV of the Periodic Table of atoms old from 22 to 40 are used, such as titanium and zirconium. The halogen can be fluorine, chlorine, bromine or iodine. but is preferably chlorine.

Typical halides of polyvalent metals that can be used according to the invention are magnesium chloride, magnesium fluoride, calcium bromide, zinc bromide, zinc chloride, barium chloride, merouriochloride, tin dichloride, tin dichloride, lead chloride, titanium tetrafluoride, titanium tetraiodide, germanium tetrachloride (cobalt) chloride, cobalt-zirconium tetrachloride (II). Chloride, nickel bromide, nickel chloride, di-

8AD ORIGIN / ^

A 54 058

Benzyltin dibromide, Dibeneylsinndiohlorid, Diaihyliinndlteonid, Diieoamyltinndichlorid, Diphenylsinndlbronid, Ithylpropylsinndichlorid, Äthyltinndriiodid and the like «

The organic hydroxy compound can have 1 to about 30 carbon atoms. Preferably, all organic hydroxy compounds use a monohydroxy compound of the general formula R-OH, in which R is a hydrocarbon group of 1 to 30, preferably about 6 to 22, carbon atoms. The hydroxyl group can be attached to an aliphatic, cycloaliphatic or aromatic hydrocarbon group. Thus, the monohydroxy hydrocarbon can be an alkanol, an alkenol, a cycloalkanol, an oyoloalkene, a phenol, a phenalkanol, an alkphenol, and the like. The Monohydroxykohlenwaeeeretoff is an alkanol, in particular a branched-chain alkanol Typical examples of such monohydroxy hydrocarbons are methanol, ethanol, propanol, Ieopropanol, Butanol, Isobutanol, 2-Ethylhexanol, Octanol, Honanol, 4,9-Dipropyldodeoanol, 3-trimethylheptanol, 3-ethylnonanol, 2-kethyl-5-isopentylhendeoanol _v dodecanol, 6,7-dipentyldodeoanol, 9,12-dimethyltioosanol, oleyl alcohol, linoleyl alcohol, 3-pentene- (2) -ol, cyolohexanol, 3-isopropylcyclohexanol, 4-decen-(1) -ol, 4-octylphenol, 4-ieopropylphenol, 4-phenyl-1-hydroxydodeoane, phenol, α-iaphthol, benzyl alcohol and the like. In the case of the invention

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$ 1

A 54 058

The organic hydroxy compounds can be driven individually or can be used together in genius. The hydrocarbon * The remainder of the organic hydroxy compound can be substituted by various groups, provided that these do not react stubborn. Typical substituent groups on the hydrocarbon radicals are nitro groups, such as in nitroalkanols, e.g. bitroethanol, and ammonium groups, such as in ammonium alkenols, e.g. the lauric acid salt of xthanolamine. ·

The temperature to be used in the process according to the invention can vary within wide limits, namely from about 10 to 120 ° C, and is preferably in the range of about 20 to 110 ° C, especially from about 25 to 105 ° C.

The molar ratio of the reactants to one another can also be vary within wide limits, e.g. from about 0.1 to 5 moles of phosphorus pentoxide and about 1 to 10 moles of the organic Hydroxy compound ^ e mole of metal halide, preferably from about 0.5 to 3 moles of phosphorus pentoxide and 2 to θ moles of the organisohen hydroxy compound per mole of metal halide. The cheapest Molar ratio varies with the particular reactants and especially with the number of halogen atoms bonded to the Fotall, as can be seen from the above general equations I bis III results. Preferably the organic hydroxy compound is made from a mixture of the metal halide and phosphorus pentoxide

- 43 -909841/1625 - - *

-, - BAD ORIGINAL

A 54 058

in an inert organic solvent at a temperature not above about 60 ° C, e.g., from about 10 to 60 ° C, geaeetate. By adding the organic hydroxy compound to one Beror-BUgt is semicircularly composed of phosphorus pentoxide and metal halide, because this limits the direct reaction of the metal halide with the organic hydroxyl compound to a minimum. Disappear due to the reaction between the metal halide and the organic hydroxy compound n & alioh free reaction sites on the Metallatoa, which otherwise

would be available for conversion to the phosphate, due to the formation of a metal salt of the hydroxy compound The initial addition of the hydroxy compound to the mixture of phosphorus pentoxide and metal halide should preferably be at Temperatures do not exceed 60 ° C and in particular at temperatures below 60 ° C, in order to prevent too high a reaction rate. Hachdem the organic hydroxy compound has been mixed with the phosphorus pentoxide and the metal halide, the reaction is preferably brought to an end by heating the reaction mixture, for example from about 80 ° C to the maximum temperatures given above, for example to about 110 ° C will. Furthermore, let it be advantageous for the discharge of the sioh to provide hydrogen halide in the reaction. At the Addition of the organic hydroxy compound to the mixture of phosphorus pentoxide and metal halide can be a stoichiometric

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■ «τ

shear excess of the hydroxy compound can be applied to to improve the yield of the desired end product. A large excess, e.g. an amount more than 1.5 times or! twice the calculated molar ratio however, the hydroxyl compound should preferably be avoided, because in many cases there is an excess of hydroxy compound will later be separated from the reaction mixture in order to desired to win © prize product *

The reaction time is "in the process according to the invention not particularly insoluble. You can range from less than 1/2 hour Ms eu 2 or 3 fagen vary and lies preferably in the range from about 2 or 3 hours up to 1 or 2 say.

Ede a3tanorganic orthophosphate can be known per se ¥ si @ a has been obtained from daia Eesktionagsmisah, e.g. through fractionated © .distillation, chromatographycha absorption and like Ss io-t jailooh also possible, if not always Two-way, the Seaktiona products as additives to £ ohlenwaaser3toff "-2r3i" batoff © n oöir Jlinaralschmlsrölen au use-, without severing sis -aus -lea Hsaktisnsgssaissh »

nsta in-srts orgLnis ^ ha IiösiaiLgsioittel for the arfindungsgsaäaso Tsrfs'area sij-; d s, B, hydrocarbons, halogenated Dry water and other solvents. Being considered "inert"

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A 54 058

denotes a solvent which takes part in relation to the Btalction! and the reaction products behave indifferently under the conditions of implementation. Suitable solvents are e.g. benzene, toluene, p-xylene, o-xylene, m-xylene, hexane, Heptane, octane, cyclohexane, methyleyolohexane, chlorobensol » Carbon tetrachloride, ethyl ether, tetrahydrofuran and the like. Preferred organic solvents are the normally liquid hydrocarbons, e.g. various aromatic, aliphatic and cycloaliphatic carbons.

In a preferred mode of operation according to the invention the equipment used for the implementation must be resistant to attack by gaseous hydrogen halide. The reaction vessel should have a heater, an aeohanic stirrer, a pressure equalization addition vessel, an indicator for the reaction temperature and an inlet for dry Compressed air must be equipped to displace the hydrogen halide formed during the reaction through a reflux condenser, through which no moisture can enter from the outside can. Bs is very useful, generally a reaction vessel with a anhydrous atmosphere to work. 2 moles of phosphorus pentoxide are evenly in a hydrocarbon, such as anhydrous n-heptane, distributed in the reaction vessel. Then 1 mole of halide of the four-

- 46 -90984t / 1625

A 54 058

Valuable metal added with sufficient stirring, among other things to prevent the material from clumping together. Finally, 6 moles of monohydroxy carbon dioxide are added from the pressure compensation vessel at such a rate that a constant evolution of hydrogen halide takes place. The temperature of the reactants is preferably kept below 60 ° C. in this process stage. After the addition has ended, the reaction participants are heated from about 80 to about 105.degree. When the evolution of hydrogen halide begins to decrease , dry air is passed through the solution in order to accelerate the displacement of the hydrogen halide vapors from the reaction vessel. When no more hydrogen halide develops, the n-heptane and the unreacted part of the hydroxy compound are distilled off in vacuo. All residue remains in the reaction vessel, the desired organometallic acid orthophosphate, which is available in yields of 95 to £ 99, based on the metal halide used.

The organometallic orthophosphates produced according to the invention are suitable as additives to fuels based on hydrocarbons, e.g. gasoline. Achieved when added to gasoline one with the organometallic orthophosphates sohon in small amounts, s.Bo of 0.01 wt .- #, rust protection effect, suppression of the surface ignition, keeping the carburetor clean, deceleration

90 9 8 * WtTB2 5 - -

ORIGINAL

A 54 058

carburetor icing and reduction of the increase dee oot number requirement. In view of their ability to reduce static friction, the organometallic orthophosphates are also suitable as wear-reducing additives Mineral lubricating oils, in concentrations of approx 1 wt .- ^ * If the organometallic orthophosphates free Having acid groups such as those prepared according to general equations I and II above, they are intended to have two grains are neutralized with an organic amine before they are used as additives to hydrocarbons The free acid groups can be neutralized, for example, by mixing with oleylamine at 30 ° C.

Typical organic orthophosphates which can be produced by the method according to the invention according to equation I are Nickel (II) - / 5i- (2-ethylhexyl) -orthophosphaj £ 7-Z ° onohydrogenmono- (2-ethylhexyl) -orthophosphat7, Nickel (II) - / 3i- (4-ootylphenyl) -orthophosphat ^ - ^ monohydrogen- mono- (4-ootylphenyl) -orthophosphaj ^, cobalt (II) - ^ £ i- (2-ethylhexyl) -orthophoephat7- / ionohydrogen-mono- (2-ethylhexyl) -orthophosphate7, lead (II) - / & l- ( 2-ethylhexyl) orthophosphate7- ^ onohydrogen-mono- (2-ethylhexyl) orthophosphate ^ 7, barium - ^ / d "i- (2-ethylhexyl) orthophosphate ^ - ,, / monohydrogen-mono» (2-ethylhexyl ) -orthophosphate /, Caloium- ^ i- (2-äthylhexyl i-orthcphocpha ^ - ^ / mOiohydrogen-mono-i 2-ethylhexyl) -orthophosi? hat7, Magnesium- ^ Ti-2-ethylhexyl) -ortho $ hoe-

- 48 -909841/1825

A 54 058

Mt

phatT '- ^ onohydrogen-inono- (2-ethylhexyl) -orthophosphate7, magnesium - / ^ - (4-octylphenyl J-orthophoaphat ^ - ^ nonohydrogen-inono- (4-ootyiphenyl) -orthophosphate7 and the same.

Typical organometallic orthophosphates that can be produced according to equation II above are titanium (IV J-bie- ^ cTi-C 2-ethylhexyl) -orthophoapha ^ 7-bis- ^ ionohydrogen ~ iDono- (2-ethylhexyl) orthophosphate /, titanium (IV / -bis- ^ cfi- (4-ootylphenyl) -orthophoephatj7-bie- ^ onohydrogen-mono- (4 ~ oc tylphenyl) -orthophoepha ^ _t titanium (r7) -biB- ^ cTi- (ethyl) -orthophoephat7-b ± s- ^ onohydrogenmono- (ethyl) -orthophosphai7, titanium (IV) - ^ d "i- (n-dodeoyl) -orthopho sphat7-bis- ^ öonohydrog en-mono- (η-do de cyl) - orthophoephajj7, titanium ( IY) -biB- ^ i- (oleyl) -or thophosphaj ^ -bie- ^ ionohydrogen-di- · oleylorthophoephate 7. Titanium (17) -bis-dibenzylorthophophate) -bie- (monohydrogen-monobenzylorthophosphate), zirconium (IV) -bie - / d "i- (2-ethylhexyl) -orthophosphate7-biB- ^ onohydrogen-nono- (2-ethylhexyl) -orthophosphate7, zirconium (IV) -bia- ^ ä" i- (4-octylphenyl) -orthophosphateT-bis - ^ monohydrogen-iBono- (4-oc tylphenyl) -orthophoepha ^, zirconium (IV) -biB <"(dioleylorthophosphate) <- bie- (monohydrogen-monooleylorthophosphate), titanium (IV) -bis- ^ jä" i- (cyclohexyl) -orthophosphate7-bis- _i / ^ onohydrogen-njono- (cyclohexyl) -orthophosphate? » Tita2i {IV} -bia- (dicresylorthophosphate) -bia- (roonohydrogsn-monocresylorthophophate), titanium (IV) -biB- (dieicoßylorthophosphate) -bis- (iDonohydrogen-monoeicosylorthophoephat), titanium (IV) -bie -, / fflono- ( isobutyl) raono- (4-oc tylphenyl) -

909βΐί / Γβ25 <*>

A 54 058. _

GrthophoBphatZ-Cmonohydrogen-monoiBObutylorthophoBpiiAtJ- ^ iono-

hydrogen-mono- (4-octylphenyl) -orthophoephat7, tin (ΪΫ) -bis - / (EM2-ethylheiyl) -orthophosphate7-bia - ^ ronohydiOgen * - "ono- (2" ethylhexyl) -orthopnoepha £ \ tin (IY ) -Ms- ^ SL- (4 * öotylphenyl) -orthopho8pha £ 7 ~ bie- ^ ^> onoIiydrogen-ZDono- (4-ootyiphtDjl) -ortliophosphat7, germanium (IV) -bie- / 3 "i- (2-ethylheiyl) -orthopho · -. pha ^ ^ bis onohydrogen-mono- (2 ~ ethylhexyl) -orthoplKiBphat7 V && like Typical examples of organometallic · Orthophoephate _f "! can be produced metals" according to the above equation III with trivalent are titanium (III J- ^ JTi- (2-äthylhexyl) -or thophospha ^ - ^ JTono-i 2-äthylheacyl) -or thophoepha ^ ⁷ , titanium (III) - / cTi- (4-octyl phenyl) -orthophoephat7- ^ ono- < 4-ootylphenyl) orthophosphate7, zirconium (IH) - ^ i- (2-ethylheacyl) -orthophosphaj ^ - ^ iono- (2-ethylhexyl) -orthophophosphate7 »xobalt (IH) - (dloleylorthophosphate) - (monooleyl orthophosphate) and the like.

Example 28

In the manner described in Example 27, a feaieoh sas 2 mol (284 g) P ₂ O ₅ and 1 mol (233 g) Zirkohiuatetraonlorid in anhydrous n-heptane with a mixture of 3.1 mol (96 g) methanol and 3, 1 mol (404 g) 2-ethylhexanol to zirconium (IV) -bis - ^ / raononiethyl-mono- (2-ethylhexyl) -or thophosphaJj7 ~ ^ SOnohydrögön-raono- {2-ethylhexyl) -orthophosphaj ^ - (aonohydrogen-eonomethylorthophoaphat ) implemented.

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Example 29

In the manner described in Example 27, H2 g (1 mol) of P ₂ O ₅ and 130 g (1 mol) of anhydrous nickel chloride are equally distributed in 1500 ml of dry octane. Then 4-30 g (3 _f 3 mol) of 2, 2 _f 4-Trimethylpentanol-1 was added. The reaction mixture is heated to 105 ° C. until the evolution of hydrogen chloride ceases. The solvent is distilled off until a temperature of 170 ° C. and a pressure of 25 m is reached one nickel (II) - / Ji- (2,2,4-trimethyl-1-pentyl) -orthophosphat7-25? ⁿ 9 ^ y ^dro een - «> a <> - (2,2,4-trimethyl-1-pentyl) orthophosphate 7

Example 30

71.0 g (0.5 mol) of phosphorus pentoxide and 65.1 g (0.25 mol) 2inn (IV) chloride are dispersed in 500 ml of toluene. To the Diapereion in toluene is a mixture of 103 g (0.5 mol) of ootylphenol and 74 »1 g (1 mol) according to the method of Example 27 Ieobutanol added. As soon as the hydrogen chloride evolution has stopped, the reaction solution is heated to 100 ° C and da * solvent distilled off under reduced pressure Da Product corresponds to the formula

- 51 -909841/1625

SZ

A 54 058

RO O,

where four of the radicals R are isobutyl groups (OHjCH (CHj) CH ₂ -) and the other two radicals R are ootylphenyl groups, / TCHjJjCCHjjO (CHj) ₂ CgHc ^, which is in accordance with the etochioeetri · see amounts of the reactants used.

Example 31

Anhydrous into a well-dispersed mixture of 14 · ι2 g (0.1 mol) of P ₂ Oe and 37.2 g (0.1 mol) in 200 Bl dibenzyltin n-heptane with good stirring, 18 g (0.3 mol) anhydrous isopropanol added. As soon as the evolution of hydrogen chloride has ceased at 98.degree. C., the solvent is distilled off under reduced pressure to a final temperature of 150.degree. A. \ s product is obtained Dibenayl8inn-bis- (nonohydrogen-monoieopropylorthophosphate) of the formula

- 52 909841/1625

S-

A 54 058

BeUUeI 52

The corresponding organometallic orthophosphoric acid phenyl-, -beneyl- and -oyclohexyleater produce when you use the 2-ethylhexanol of Example 27 replaced by equivalent amounts of phenol, benzyl alcohol or cyclohexanol.

- 53 -. . - BATHROOM.

909841/1825

Claims (1)

156 & 247 A 54 058 10 February 1966 Claims 1 · Process for the production of organometallic compounds of orthophosphoric acid esters, characterized in that Phosphorus pentoxide, a halide of a polyvalent metal containing at least two halogen atoms, and an organic one Hydroxy compound having 1 to about 30 carbon atoms in the molecule in an inert organic solvent with each other to be implemented » 2. The method according to claim 1, characterized in that the reaction is carried out at about 10 to 120 ° C. 3. The method according to claim 2, characterized in that the reaction is carried out at about 20 to 110 ° C * 4. The method naoh claim 1 to 3 * characterized in that the organic hydroxy compound is introduced into a mixture of the halide of the polyvalent metal and phosphorus pentoxide in the inert organic solvent. 9O.m $ / 1625 SS A 54 058 5. The method according to claim 4 »characterized in that dit organic hydroxy compound to the Gemieoh at about 10 bie 60 ° 0 added and after the addition the Genisch on a tea temperature of about 80 to 110 ° O is maintained. 6. The method according to claim 1 to 5, characterized in that daes a Monohydroxykohlenwaaaeratoff is used as the organic hydroxy compound. , 7t method according to claim 6, characterized in that about 2 to 8 Hols of monohydroxy carbon and about 0.5 to 3 Hol phosphorus pentoxide reacted with 1 mole of metal halide will. 8. The method according to claim 7, characterized in that about 6 moles of monohydroxy carbon dioxide and about 2 moles of phosphorus pentoxide are reacted with 1 mole of metal halide. 9. The method according to claim 1 to 8, characterized in that the metal halide used is a halide of a metal from Group II, IV, VI or VIII of the Periodic Table. TO. The method according to claim 9, characterized in that a Halide of a metal of Group IV of the Periodic Table with an atomic number of 22 to 40 is used. 909841/1625 ORIGINAL SS A 54 058 11 · The method of claim 1 to 8, daduroh in DAAs a halide of a polyvalent metal dor general formula MX _n is used, where M is the polyvalent metal, X is a halogen atom and the valence of the metals η * £ mean " 12. The method according to claim 11, characterized in that a Halide of a tetravalent metal is used « 13 «A method NaOH to claim 12, characterized _f daduroh that a halide of zirconium or titanium is used. 14. The method according to claim 11 to 13t, characterized in that that a chloride is used as the metal halide. 15 * Method according to claim 12, characterized in that a organometallic compound of the general formula RO. RO ' Il "P-O- ■ OR "OH is produced in which M is a tetravalent metal and R is a Means hydrocarbon radical having 1 to about 30 carbon atoms. - 56 909541/1625 A 54 058 16. The method according to claim 11, characterized in that a halide of a divalent metal is used. 17. The method according to claim 16, characterized in that a metal organ! βehe compound of the general formula 0 0 L · ⁰ * > p - ο - M - 0 - ΚΓ OH R- (T is produced, in which H is a divalent metal and H is a carbon hydrogen creature with 1 to about 30 carbon atoms. 18. The method according to claim 11, characterized in that a Halide of a trivalent metal is used 19 · Procedure naoh Anaprach 18; daduroh marked that an organometallic compound of the general formula T-OB is produced, in which H is a trivalent metal and R a Eohlenwaaaeratoffreßt with 1 bia about 50 carbon atoms » 909841/1625 - 57 - A 54 058 J » 20. The method according to claim 6 to 14, characterized in that as monohydroxy carbon hydrogen, an alkanol, a phenylalkenol or an alkyl phenol is used. 21. The method according to claim 20, characterized in that an alkanol with 6 to about 22 carbon atoms in the molecule is used as the monohydroxy hydrocarbon. 22 »The method according to claim 20, characterized in that as Alkanol 2-ethylhexanol is used. 25t method according to claim 1 to 22, characterized in that an inert hydrocarbon is used as the inert organic solvent. 24. Process for the preparation of metal compounds of acidic hydrocarbon orthophosphates, in which in an inert organic Solvent a mono- (hydrocarbon) -dihydrogen-or'thophosphat or a mixture of a mono- (hydrocarbon) dihydrogen orthophosphate and a di (hydrocarbon) monohydrogen orthophosphate with a halide of a polyvalent metal is implemented, characterized »that the metal halide is the halide of a metal of the group IV B of the Periodic System and the orthophosphate used is one in which the hydrocarbon radicals are each 1 contain up to about 30 carbon atoms. 90 ^^ 41/1625 A 54 058 si 25. The method according to claim 24-1, characterized in that the Reaction is carried out at about 10 "to 120 ° C. 26. The method according to claim 25 »characterized in that the Implementation "is carried out at about 40 to 110 ° 0. 27. The method according to claim 24 to 26, characterized in that phosphoric acid esters with branched-chain hydrocarbon groups are used. 28. The method according to claim 27, characterized in that Phosphoric acid esters with branched-chain alkyl groups can be used. 29 ". Method according to Claim 28, characterized in that Phoephoric acid 2-ethylhexyl ester can be used. 30. The method according to claim 27 to 29, characterized by that phosphoric acid ester with Kohlenwaseeratoffgruppen of about 6 to 22 carbon atoms can be used. * Method according to claim 24 to 30, characterized in that . =? das0 as a metal halide, a halide of tetravalent titanium is used". - 59 - 8AD ORIGINAL A 54 058 32. Process for the preparation of amine salts of metal compounds of acidic hydrocarbon orthophosphates, characterized in that an amine with an acidic metal-carbon hydrogen-orthophosphete of the general formula / "(0H) (OR) 0P0-_7 _n M / ~ -0P0 (OR) ₂ J ^ ₁ in which R is a hydrocarbon group with 1 to about 30 carbon atoms, M is a metal from Group IV B of the Periodic Table, η is an integer from 1 to 4 and n * is an integer from 0 to 3 and the sum η + η ^{1 is the} same as the valence of the metal M. 33 «Method according to claim 32, characterized in that the amine used is an aliphatic amine of about 6 to 24 carbon atoms and the sum η + n ^f « 4. 34 «Method according to claim 32, characterized in that as AaIn an alkenylamine is used. 35 * Procedure naoh Anepruoh 32, known as a Aain a Dlamin is used. 36. The method according to claim 32 to 35, characterized in that η a 2 and η ¹ » e 37. The method according to Ansprush J2 to 35, characterized in that that η «4 and η ¹ = C. 909841/1625 ⁸⁴⁰ A 54 058 38. The method according to claim 32 to 37, characterized in that orthophosphoric acid derivatives are used in which each residue is a branched-chain hydrocarbon group means having about 6 to 22 carbon atoms. 39ί The method according to claim 38, characterized in that Orthophosphoric acid derivatives are used in which the R © ine denotes a branched-chain alkyl group. 40. The method according to claim 38 _9, characterized in that Orthophosphorsäureueriirate are used in which the radical R is a 2 ~ ethylhaxyl group. 41. The method according to claim 32 to 40, characterized in that a halide of titanium is used as the metal halide will. 4 ^ = motor fuel or Sehmisröl based on a liquid Hydrocarbon content, characterized by a content on a small Msng® © ines alain salt of a metal bond an acidic hydrocarbon orthophosphate, wherein the metal is a Group IV B metal of the Periodic Table. 43ο liquid hydrocarbon product according to claim 42, dadureh characterized that the metal bond of the acidic carbon 909841/1625 'bad OR.GiNAL - 61 - A 54 058 hydrogen orthophosphates the general formula Z ^- (OH) (OR) OPO- J _n M / "- 0PO (OR) ₂ JT _n , in which R is a hydrocarbon group with 1 to about 30 carbon atoms, H is a metal from Group IV B of the Periodic System, η is an integer from 1 to 4 »n ^{1 is} an integer from 0 to 3 and the sum η + n ^{1 is} equal to the valence of the metal M. 44 · Liquid hydrocarbon product according to claim 43 »thereby characterized that R means a branched-chain hydrocarbon group » 45 * Liquid hydrocarbon product according to claim 43 or 44, characterized in that R is an alkyl group. 46. Liquid hydrocarbon product according to claim 43 to 45t characterized in that the radical R contains 6 to 24 carbon atoms » 47 · Liquid hydrocarbon product according to claims 43 to 46, characterized in that the radical R is a 2-ethylhexyl group. 48. Liquid hydrocarbon product according to claim 43 to 47, characterized in that η = 2 and η ¹ »2. -62- A 54 05β 49. liquid KohleuwaaseratofferzeugniB NaOH claim 43 bie 46, characterized in that η "4 and η ^1" · 0 let 50 liquid hydrocarbon product according to claim 43 Ms 46, characterized in that M is a tetravalent metal. 51. Liquid hydrocarbon product according to claims 43 to 50 » characterized in that M means titanium « 52. Liquid hydrocarbon product according to claims 42 to 51 » characterized in that the amine is an aliphatic hydrocarbon amine is. 53. Liquid hydrocarbon product according to claim 52, characterized characterized in that the amine has 6 to about 24 carbon atoms contains. 54. Liquid hydrocarbon product according to claim 52 or 53 » characterized in that the amine is an alkenylamine. 55 * Liquid hydrocarbon product according to claim 54, characterized characterized in that the alkenylamine is oleylamine. 56. Plus hydrocarbon product according to claim 52 or 53 » characterized in that the amine is a diamine. 9098U / J625. ~, _ _£ BAD ORJGiNAL A 54 058 57 · Liquid hydrocarbon drink according to claim 56, characterized characterized in that the dianine is N-oleyl-1,3-propylenediaain 58. Liquid hydrocarbon product according to claim 52 or 53 » daduroh indicated that the amine is an alkylamine. 59 · Liquid hydrocarbon product according to claim 52 or 53t daduroh characterized in that the amine is "coconut ^H -amine · 60. Liquid hydrocarbon product according to claims 42 to 59ι characterized in that the base is a benein 61. Liquid hydrocarbon product according to Claim 60 _v daduroh characterized in that it contains the Aeinsalz in sufficient quantities to delay rust formation. 62. Liquid hydrocarbon product naoh claim 60, daduroh characterized in that it contains the anine salt in amounts of about 0.001 to 0.05 wt. 63 * Liquid hydrocarbon product according to claims 42 to 59 » daduroh indicated that the base is a lubricating oil. 64. Liquid hydrocarbon product according to Anspruoh '63, daduroh characterized in that the lubricating oil is a mineral oil. 909641/1625 A 54 058 65. Liquid hydrocarbon product according to claim 63 or 64 thereby gelcennzeiohnet that it contains the amine salt in sufficient Contains quantities to reduce the wear and tear of the oil to rent. - 65 - 909841/1625 BATH