FR2470155A1 - COMPOSITIONS CONTAINING SALTS AND COMPLEXES OF ALKYLATED AMINOPHENOLS METALS OR METALLOIDS AND LUBRICANT CONTAINING THEM - Google Patents

Abstract

THE INVENTION RELATES TO SALTS AND COMPLEXES OF METALS OR METALLOIDS OF ALCOHOLIC AROMATIC COMPOUNDS CARRYING HYDROXY AND AMINO SUBSTITUENTS WHICH ARE USEFUL AS ADDITIVES FOR LUBRICANTS AND FUELS. THE ALCOYL GROUP IN THESE SALTS OR COMPLEXES CONTAINS AT LEAST 30 ATOMS OF ALIPHATIC CARBON. WE PREFER THE SALTS AND COMPLEXES OF ALCOHOLIC AMINOPHENOLS. THEY MAY BE PREPARED FROM FREE ALCOHYL AMINOPHENOL OR BY REDUCTION OF A SALT OF THE CORRESPONDING ALKYL NITROPHENOL. ALSO USEFUL ARE THE REACTION PRODUCTS OF SUCH SALTS OR COMPLEXES WITH FORMALDEHYDE REAGENTS.

Description

The present invention relates to new com

material positions useful for lubricants and fuels. In its most general sense, it comprises salts and complexes of metals and metalloids of at least one aminophenol of the formula (OH) c (R) a- L- (NHa in which: Ar is an aromatic radical n ' having no sulfur or amino bonds between its aromatic rings;

  R is a hydrocarbon-based radical sensitive to

fully saturated with at least 30 carbon atoms

  phatic; and a, b and c are each an integer ranging

from 1 to three times the number of aromatic rings in Ar.

In the above formula, Ar is an aromatic radical which may be monocyclic or polycyclic and which may or may not contain hetero atoms such

  than oxygen, nitrogen or sulfur. Examples of

  monocyclic aromatic poses from which Ar can be

rivé are benzene, pyridine, thiophene, furan,

etc. The polycyclic compounds can be of the type with no-

  condensed water such as naphthalene, anthracene, phenan

threne, indole and carbazole. They can also be

  of the type with linked nuclei as long as the connections do not

do not hold sulfur or nitrogen atoms of the amino group;

  examples of polycyclic compounds with appropriately linked nuclei

required are biphenyl, phenyl oxide, benzopheno-

  ne and diphenylmethane. Other suitable Ar radicals are derived from polycyclic compounds containing more than one

  bridge between the nuclei (eg fluorene). The radi-

preferred Ar cals, however, are the monocyclic radicals

  especially the monocyclic carbocyclic radicals

  ques. Particularly preferred are the compounds in the-

which Ar is a "phenyl-based" radical (as defined

below) and especially a phenyl radical.

The radical R is a radical based on hydrocarbon-

re essentially saturated having at least 30 atoms of

  aliphatic bone. As used herein, the term "hydrocarbon-based radical" means a radical having a carbon atom bonded directly to the rest of the molecule and having a predominantly hydrocarbon character

in the context of the present invention. Such ra-

  dicals include the following: (1) Hydrocarbon radicals; that is to say aliphatic radicals (for example alkyl or alkenyl) and aliphatic radicals with aromatic or alicyclic substitution. (2) radicals of substituted hydrocarbons;

  that is to say radicals containing non-substituents

  which, in the context of this invention,

  tion, do not alter the primarily hydro-

  carbide of the radical. Appropriate substituents are well known to those skilled in the art (e.g. hydroxy, halo,

  carbalcoxy, nitro, sulfonic acid ester).

(3) Hetero radicals; that is to say radi-

  which, although having a mainly hydro-

carbide in the context of the present invention, contains

atoms other than carbon present in a

  chain or nucleus otherwise composed of carbon atoms

born. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen,

oxygen and sulfur.

In general, there will be no more than about three substituents or heteroatoms, and preferably no more

of one, for 10 carbon atoms in the radical based on hy-

drocarbon. The expression "phenyl radical" has a meaning analogous to that given above with respect to

phenyl radical.

  The radical R can contain up to approximately 750 (preferably from approximately 40 to approximately 500) carbon atoms

  aliphatic. Many suitable R radicals are derived

of polymers of mono-olefins and / or of di-olefins

containing from 2 to 10 carbon atoms, such as ethylene, propylene, 1butene, isobutene, butadiene, etc. Polymers of 1-mono-olefins, and especially of mixtures of butenes mainly comprising isobutene, are preferred. The radical R can also be derived from a

halogenated polymer (usually chlorinated or brominated and specific

especially chlorinated) of this type. Other appropriate sources

  of the radical R are monomeric alkenes of molecular weight

high area like 1-tetracontene and their chlo- derivatives

res, aliphatic petroleum fractions such as paraffin waxes, white oils, etc. The radicals R are substantially aliphatic; that is, they do not contain more than one non-aliphatic substituent (for example aromatic or alicyclic) of 6 carbon atoms or less for 10 aliphatic carbon atoms. Preferably, they do not contain more than one such non-aliphatic group per 50 carbon atoms, and in most cases they do not contain at all

non-aliphatic groups; that is, R is ty-

  bitingly aliphatic. It is also substantially saturated;

that is, it does not contain more than one double bond

its carbon-carbon for 10 simple carbon-carbon bonds.

  The particularly preferred radicals R are radicals

alkyl and monoalkenyl.

  As will be evident from the formula below

above, the aminophenols from which the compositions are derived

according to the present invention contain at least one of each

  none of the R, hydroxy and amino groups. They can contain more than one of any or all of these groups, the upper limit being a situation in which each of the indices a, b and c is three times the number of aromatic rings in Ar. Usually, however , at

  and b are each 1 and b is 1 or 2, most often 1 too.

  Thus, the preferred aminophenols are those derived from an a-

24? O1SS

monocyclic monocyclic minophenol. In such compo-

  ses, R can be in ortho, meta or para position compared to

  has a hydroxy group, but is usually in the para position. The term "metal" is used herein in its current physical and chemical sense and denotes elements having the physical and chemical properties of metals. The term "metalloid" designates elements having properties

  intermediates between metals and non-metals and com-

  takes things like boron and silicon. The com-

  positions included in the general framework of this in-

vention include salts and complexes of metals and metalloids. Most compositions containing metals are described very precisely as being salts, while those containing metalloids are most often described in a more precise manner as being complexes. In some cases, however, the compositions

  may have certain characteristics of a salt and some

taines of a complex and their precise chemical nature at this

  About is considered unimportant.

  The preferred metals and metalloids in the compositions according to the present invention are the metals of groups IA, IIA and IIB, iron, cobalt, nickel, manganese, silicon, boron, aluminum, chromium, tin, molybdenum, tungsten, antimony, lead,

copper and bismuth. We especially prefer the

levels of groups IA, IIA and IIB and more especially sodium, potassium, magnesium, calcium, barium

and zinc.

The metal salts according to the present invention

  can be conveniently prepared by the reaction of the friend

  nophenol with a reactive metal or a reactive metal compound. Suitable aminophenols can be prepared by nitration of a corresponding hydroxyaromatic compound

and reducing the nitro group to an amino group. The reaction

  tion of nitration is known in the art and agents

247'0 55

suitable reducing agents for nitro aromatic compounds are also known; they include hydrazine, carbon monoxide and hydrogen, which are commonly used

  in the presence of metallic catalysts such as palla-

  dium, platinum and its oxides, nickel or copper chromite. Appropriate processes for preparation

of these aminophenols are described in the U.S. Patent.

NO 4 100 082, which is hereby incorporated by reference for

its description of such processes.

Examples of reactive metal compounds which can be reacted with the aminophenols described

  above to produce salts according to the present invention

tion are lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate , the oxide of

  potassium, potassium hydroxide, carbonate of po-

tassium, potassium methylate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium methylate, magnesium propylate, salt

  magnesium ethylene glycol monomethyl ether

  cervix, calcium oxide, calcium hydroxide, carbo-

  calcium nate, calcium methylate, propylate

calcium, calcium pentylate, zinc oxide, hydro-

  zinc xyde, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, oxide

cadmium, cadmium hydroxide, cadmium carbonate

mium, cadmium ethylate, barium oxide, hydroxy-

barium, barium carbonate, barium ethylate, barium pentylate, aluminum oxide, isopropylate

aluminum, cupric acetate, lead oxide, hy-

  lead hydroxide, lead carbonate, tin oxide, tin butylate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide, chloride

  nickel, nickel carbonate and chromium (II) acetate.

2470 155

The salts according to the present invention can be

be acidic, neutral or basic salts. By "acid salt",

denotes a compound in which the phenolic hydroxyls

  that not all have been transformed into salt groups.

  Thus, an acid salt can contain a hydroxy group li-

bre and an oxy-metal group in its molecular structure.

  Such a salt can be represented by the formula OM

H2N OH

in which M is an equivalent of a metal ion and

  R is as defined above. A dival metal salt

  slow can result from the reaction, for example, of two moles of a diphenol with one mole of a compound of a divalent metal (eg calcium, barium, zinc or lead). Acid salts are ordinarily prepared from a reaction mixture containing less than 1 and usually more than 1/2 equivalent of metal compound

per equivalent of aminophenol.

  By "neutral salt" is meant a compound in

  which all phenolic hydroxyls have been transformed

  més in groups of salt. Neutral salts can be prepared by reacting 1 equivalent of aminophenol with 1 equivalent (or very slightly more, such as 1.1

equivalent) of the metal compound.

The reaction between the alkylated aminophenol and the reactive metal compound is usually carried out between room temperature and the decomposition temperature of the reaction mixture, preferably between about 300C and about 1500C. It is frequently preferred to carry out the reaction in a substantially inert normally liquid organic diluent such as toluene, mineral oil, ethanol, isooctyl alcohol, etc.

  to facilitate contact between the metal compound and the a-

  alkylated minophenol. After salt formation, the materials

  volatile res can be distilled off if desired and the product, which can be collected as a solution in a non-volatile diluent such as mineral oil, can be subjected to operations

known such as filtration.

  In some cases, more metal

less than the stoichiometric amount can react with

  aminophenol to form a basic salt. A "basic salt"

that "is therefore a salt in which the metal is present in amounts stoichiometrically in excess with respect to

phenolic hydroxyls. Such basic salts are characteristic

terized by a metal ratio substantially greater than 1. The term "metal ratio" as used herein means the ratio of the total of metal equivalents in

  salt equivalent to organic anion in this salt. Ain-

if, it is a measure of the stoichiometric excess of metal in a metal salt of an organic acid compound. For example, a basic salt can be obtained by the reaction

  (under conditions similar to those described above-

  above about acidic and neutral salts) of 1 equivalent of an aminophenol with 2 equivalents of a metal compound;

such a salt will have a metal ratio of 2.

  In the preparation of basic metal salts,

it is sometimes advantageous to process the reaction mixture

tional, in the presence of a promoter, by an acid gas such

that carbon dioxide at a temperature between-

  about 2000 and the reflux temperature of the mixture.

  This carbonation step is known in the prior art. Examples of suitable promoters are

  lower alcohols, for example methanol or pro-

  panol, and phenolic compounds, for example heptyl-

  phenol or octylphenol. For example, a basic calcium salt having a metal ratio greater than 1 can be prepared by reacting 1 equivalent of an aminophenol

with more than 1 equivalent of calcium hydroxide and in car-

  bonatant the mixture in the presence of methanol. The stage of

carbonation is not absolutely necessary in the pre-

paration of basic salts, but it is advantageous in that it allows the incorporation of appreciably more metal in the product and can have a clarifying effect.

both on the manufacturing mixture and on the product.

  The carbon dioxide treatment is carried out so as to substantially reduce the titratable basicity of the reaction mass. There are basically

  two materials in the reaction mass before carbona-

  which are susceptible to reaction with carbon dioxide; the free basic metal compound (the one that

is excess compared to the stoichiometric quantity ne-

necessary to form the normal metal salt) and the salt

  normal metal. It is possible that each of these

  third reacts simultaneously with carbon dioxide, but it is more likely that the basic compound of the excess metal is carbonated first and the normal salt of the metal

is then carbonated.

The metal salts according to the present invention can also be prepared by double decomposition; for example, an aminophenol can be reacted with a basic alkali metal compound and the resulting alkali metal phenate can then be reacted with a metal halide (e.g. zinc chloride) to

give the desired metal salt.

  Metalloid complexes according to the present invention are conveniently prepared by the reaction of a reactive metalloid compound such as boric acid or tetraethyl silicate with alkylated aminophenol at a temperature between room temperature and the decomposition temperature of the reaction mixture and

typically between about 50WC and about 2250C. On the way

  laughing, the metalloid compound can be reacted with the alkylated nitrophenol and the resulting product is reduced so as to give the aminophenol complex as

as previously described.

  According to another method for preparing the compounds

sitions of the present invention, an alkylated nitrophenol is

reacted with a reactive metal or metal compound

  rigid and a reducing agent other than elemental sulfur

re, usually one of the reducing agents described above

  above. Both reactions can be carried out simul-

temporarily or reduction may follow salt formation

  nitrophenol. In addition, the operating methods can

may be substantially the same as those described above

  known for the formation of the aminophenol salt and the reduction

  free nitrophenol, respectively.

  Also included within the general scope of the invention are compositions prepared by reacting the salts or complexes of metals or metalloids described.

  above with a formaldehyde generating reagent

  me formaldehyde itself, aqueous solutions of formaldehyde, paraformaldehyde or trioxane. The reaction with the formaldehyde-generating reagent is typically carried out between approximately 65WC and approximately 1501C and can involve between approximately 0.5 and approximately 2.0 equivalents of formaldehyde per equivalent of salt or

  complex. (In this regard, the equivalent weight of formal-

hyde is equal to its molecular weight and that of the salt or complex is its molecular weight divided by the number

aromatic nuclei present).

The precise molecular structure of the salts and complexes according to the present invention is not known with certainty. Some of the metal salts (for example) may be simple phenates, while others may be chelated with the

  amino group. It is believed that the structural details mo-

  are not critical to the present invention.

tion. The preparation of salts and complexes according to the

The present invention is illustrated by the following examples.

All parts are by weight, unless otherwise indicated.

Example 1

  An alkylphenol is prepared by reacting, in the presence of a boron-phenol trifluororic complex, phenol with a polybutene having a number average molecular weight (as determined by osmometry in the vapor phase) of approximately 1000 and mainly comprising mesh

isobutene. To a solution of 609 parts of this alkyl-

  phenol in 450 parts of mineral oil, we add to

58-63 C approximately, in 8 hours, 46.5 parts of ni-

  stick. The mixture is stirred for 1 hour 1/2 at the same time.

temperature and then it is heated to 142 ° C. and nitrogen is blown into it for approximately 1 hour and a half. We

then heats to 143-145 C while the volatile

  tiles are removed by distillation. We filter the pro-

  residual product to obtain a solution in the oil of a

alkylated nitrophenol.

  12 parts of hydrazine (64%) are added, in 6

  1/4 hours, at 160 C, at 320 parts of the nitro- solution

alkylated phenol. We filter the product to obtain a

  oil solution of an alkylated aminophenol.

At 1863 grams of the solution of aminophenol al-

coylé, add 29.1 grams (an equivalent amount) of

  lithium hydroxide monohydrate and 150 cm3 of iso- alcohol

  propyl. The mixture is heated to reflux, stirred for 2 hours and then subjected to stripping.

under vacuum at around 160 C to remove volatile matter

  tiles. The residue is filtered to obtain a solution in

  the oil of the desired lithium salt of the alkylated aminophenol.

The product contains 1.97% lithium.

Example 2

  A solution of 18.4% is slowly added

  parts of nitric acid in 35 parts of water to a solution of 265 parts of the alkylphenol of Example 1, 176 parts of oil and 42 parts of petroleum naphtha having a boiling point of 20 C about. We stir the mixture

for 3 hours at about 30-45 C and then submit it

te a vacuum stripping to obtain a solution

in the oil of an alkylated phenol.

A mixture of 1500 parts of the solution of alkylated nitrophenol, of 642 parts of isopropyl alcohol

  that and 7.5 parts of a nickel catalyst on kiesel-

guhr is purged with nitrogen and hydrogenated at 7 dN / cm2 for 14.5 hours. It is then again purged with nitrogen, filtered and subjected to vacuum stripping to give

  a solution in mineral oil of an aminophenol al-

coylé. A solution of magnesium salt is prepared by dissolving 324 parts of magnesium in 6000 parts

  ethylene glycol monomethyl ether. We prepare

re a solution of 336 parts-of the amino solution-

  alkylated phenol in 150 parts of toluene and we add

parts of the magnesium salt in 3 minutes at 56-62 C.

The mixture is heated with stirring at 55-70 C for about 2 hours; 2 parts of water are then added and heating is continued at 112 C (the reflux temperature) for approximately 3 3/4 hours. Carbon dioxide is then blown into the mixture for 2 1/2 hours at 63-65 C and the mixture is subjected to stripping

  under vacuum. By filtration at 155 ° C., a solution is obtained.

  tion in oil of the desired basic magnesium salt of the alkylated aminophenol; it contains 8.85% ash

magnesium sulfate.

Example 3

  Magnesium methylate in solution is prepared

  touting 13.8 parts of magnesium in 1000 parts of metha-

  nol. Carbon dioxide is blown into the pro-

delivers until reaction stops and in 6 minutes

  1100 parts of the aminophenol solution are added.

  coylé of example 1. The mixture is heated to 90 C while

by injecting nitrogen into it; 300 parts of al are added

  cool isooctylic and heating continues at 150 C.

2470 155

  Water is then blown into the mixture for approximately 20 minutes, the mixture is stripped under vacuum and filtered while it is still hot. The filtrate is an oil solution of the desired basic magnesium salt. It contains 6.27%

* magnesium sulfate ash.

Example 4

To a mixture of 1555 parts of an alkylated nitrophenol solution prepared as described in Example 1, of 175 parts of a mixture of isobutyl and amyl alcohols and of 75 parts of water, the following is added at 550C,

  with stirring, 31 parts of calcium hydroxide. We heat-

fe the mixture at reflux for 3 hours and then

  the stripping of volatile matter at 125-1600C, the operation-

The final stripping is carried out under vacuum. The residue is filtered to obtain a solution in oil

  of a calcium salt of the alkylated nitrophenol.

  85 parts of the calcium salt described above

  above, 45 parts of isopropyl alcohol and 50 parts of toluene are added. Catalytic platinum, 0.04 part, is added, and the solution is pressurized with 2.5-3.9 dN / cm 2 of hydrogen and shaken for approximately 7 hours. The hydrogenated mixture is filtered and the filtrate is subjected to vacuum stripping; finally we filter

  the residue - to obtain a solution in the salt oil -

basic calcium desired from alkylated aminophenol. The

product contains 3.28% calcium sulfate ash.

Example 5

  An alkylphenol is prepared substantially as described in Example 1 by reacting phenol with a polybutene having a number average molecular weight.

About 600 (as determined by step chromatography-

  wise through a gel) and comprising mainly isobutene meshes. To a mixture of 2420 parts of this alkylphenol and 900 parts of petrol for textiles,

  adding in 2 hours, with stirring, at 30-351C, a solution

tion of 270 parts of nitric acid in 300 parts of water. The mixture is stirred at 300C for 3.5 hours and then subjected to stripping under vacuum to

obtain an alkylated nitrophenol.

  To a mixture of 625 parts of nitrophenol

alkylated, 105 parts of toluene, 70 parts of meta

  thanol and 280 parts of mineral oil, is added to 350C, with stirring, 91 parts of calcium hydroxide. We

breathes carbon dioxide into the mixture at 51-

  560C for about 50 minutes, the mixture is subjected to vacuum stripping and filtered to obtain a

basic carbonate calcium salt of nitrophenol.

  Platinum oxide, 0.4 parts, is added to a mixture of 120 parts of the basic calcium salt of

  alkylated nitrophenol, 50 parts of isopropyl alcohol

  than and 40 parts of toluene. The mixture is pressurized with 46 parts of hydrogen, it is heated to

500C and shake it for about 3 1/2 hours. In-

it is then filtered, subjected to vacuum stripping and filtered again to obtain a solution in

the oil of the basic calcium carbonate salt of aminophé

  alcoylé nol. The product contains 3.91% sulphate ash

calcium fate.

E: example 6

  A mixture of 1090 parts of a solution of a-

alkylated minophenol prepared as described in Example 2 and 21 parts of calcium hydroxide is heated to

700C, while shaking, for 10 minutes. We added

  then paraformaldehyde (37% aqueous solution), 61 parts, and the mixture is heated to reflux for 1 hour, after which the volatiles are removed by blowing nitrogen at 1550C. By filtration, the desired solution in oil is obtained of a calcium salt with formaldehyde bridge of the alkylated aminophenol. The product

contains 2.5% calcium sulfate ash.

Example 7

A mixture of '306 grams of a solution of a-

  alkylated minophenol prepared as described in the example

  2, 10 grams of barium oxide and 25 cm3 of metha-

nol is heated at reflux for 4 hours, after which the volatiles are removed by distillation followed by stripping in vacuo. After filtration,

  obtains an oil solution of barium salt

sire; the product contains 5.59% sulphate ash

barium.

Example 8

  To a mixture of 500 grams of a solution of a-

  alkylated minophenol prepared as in Example 2 and

  cm3 of methanol, added in portions at 50 ° C., with

  so energetically, 61 grams of barium oxide. The mixture is heated at reflux for 1 hour and a half, after which the volatiles are removed by stripping under vacuum. After filtration, an oil solution of the basic barium salt desired of the alkylated aminophenol is obtained. The product contains 6.8% sulfate ash

barium.

Example 9

  A mixture of 706 grams of an ami solution

  alkylated nophenol prepared as in Example 1 and of

70 cm 3 of methanol is heated to 50 ° C. and 98 grams of barium oxide are slowly added. We heat at reflux

mixing for 2 hours, after which the materials

latiles are removed by vacuum stripping. Toluene, 700 cc, is added, and the mixture is filtered, after which the toluene is removed by stripping in vacuo. The product is the desired solution in oil of a basic barium salt of alkylated aminophenol. It contains 8.29% of

barium sulfate ash.

Example 10

A mixture of 222 parts of an ami solution

alkylated nophenol prepared as in Example 1 and 10

  parts of cupric acetate monohydrate is heated during

for 12 hours at 100-160 C, after which all volatile matter

  tiles are removed by vacuum stripping. The residue is filtered to obtain an oil solution of the desired copper salt containing 2.45% copper.

Example 11

  A mixture of 222 parts of an amino solution

  alkylated phenol prepared as in Example 1 and 12.3 parts of chromium (II) acetate monohydrate is heated

  at 100-160 C for 12 hours and then subjected to a strip-

  page under vacuum. The residue is filtered to obtain the solution.

  desired content in the oil of a chromium salt which contains

0.035% chromium.

Example 12

  A mixture of 512 parts of an amino solution

  alkylated phenol prepared as in Example 2, of 16 parts

  zinc oxide and 100 parts ethanol is heated

  fairy at reflux for 3 hours and then at 140 C while

  that the volatiles are removed by distillation.

  It is finally subjected to vacuum stripping and filtered to give an oil solution of the desired zinc salt.

aminophenol which contains 0.18% zinc.

Example 13

  A 658 parts of a solution of aminophenol al-

  coylé prepared as in Example 1, 10 ml are added

  nutes at 60 C, under nitrogen, 24 parts of a 50% solution of sodium hydroxide. The mixture is stirred for 1 hour at 60 ° C. and then 36 parts of hexahydrate are added.

  nickel (II) chloride in 10 minutes, with stirring. We have-

  the mixture is stirred for 3 hours at 80 ° C. and then nitrogen is blown into it and subjected to stripping under vacuum to remove the volatile matter. After filtration, an oil solution of the nickel salt is obtained

desired containing 1.2% nickel.

Example 14

  A mixture of 1233 parts of the amino solution

  alkylated phenol of Example 1 and 20.4 parts of boric acid is heated to 1801C and nitrogen is blown into it

  during 2 hours. After vacuum stripping and filtering

  tion, the desired boron-containing complex is obtained from the alkylated aminophenol which contains 0.26% boron.

Example 1 5

  A product similar to that of Example 14

is prepared from 1486 parts of the ami solution

  alkylated nophenol and 443 parts of boric acid. he

contains 4.35% boron.

Example 16

A mixture of 1405 parts of the a- solution

alkylated minophenol of Example 1 and 76.2 parts of i

  aluminum sopropylate is heated for 3 hours at 155-195WC while the volatiles are removed by distillation. It is then subjected to vacuum stripping and filtered to give the desired product containing

0.72% aluminum.

  The compositions according to the present invention are useful as additives for lubricants and fuels, in which they act mainly as detergents and dispersants for suspending

and remove deposits, mud, etc. We can use them

  use in various lubricants based on various oils

of a lubricating viscosity, comprising lubricating oils

  natural and synthetic fibers and their mixtures. These lubricants include lubricating oils for spark ignition internal combustion engines and

  compression ignition, including auto engines

mobile and truck, two-stroke engines (in the-

which compositions are particularly useful), aircraft piston engines, marine and railway diesel engines, etc. They can also be used in

gas engines, stationary generators, turbines

  bines, etc. Fluids for automatic transmissions, lubricants for combined rear axle gearbox assembly, lubricants for gears, lubricants

for metal work, hydraulic fluids and other

  very lubricating oil and grease compositions can also be improved by incorporating the compositions according to the present invention. Natural oils include animal oils and vegetable oils (e.g.

  castor oil, bacon oil) as well as petroleum oils

  quides and lubricating oils treated with solvent or treated with acid of paraffinic, naphthenic or

  paraffinic-naphthenic mixed. Oils of a viscous

lubricating sity derived from coal or shale

  are also useful base oils. Lubricated oils

synthetic flakes include hydrocarbon oils

res and halogenated hydrocarbon oils such as polymerized and interpolymerized olefins (for example polybutylenes, polypropylenes, copolymers

  propylene-isobutylene, chlorinated polybutylenes, poly-

  (1-hexenes), poly (l-octenes), poly (l-decenes),

etc., and their mixtures_7; alkylbenzenes _ for example-

  full of dodecylbenzenes, tetradecylbenzenes, di-

nonylbenzenes, di- (2-ethylhexyl) benzenes, etc.7; polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl oxides and alkylated diphenyl sulfides and their derivatives, analogs, homologs, etc.

  Polymers and interpolymers of aluminum oxide

  coylene and their derivatives in which the hydro-

xyle terminals have been modified by esterification, ether-

another class of lubricating oils, etc.

  known synthetic lubricants. Examples are the oils prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (for example ether

polyisopropylene glycol methyl having a molecular weight

average ring of 1000, polyethylene diphenyl ether

  ne-glycol having a molecular weight of 500-1000, ether

  polypropylene glycol diethyl having a molecular weight

cular of 1000-1500, etc.) or their mono- and poly- esters

  carboxylic, for example acetic acid esters, mixed C3-C8 fatty acid esters or the diester

  of C13 oxo acid of tetraethylene glycol.

Another suitable class of lubricating oils

  your synthetics includes esters of dicarboxylic acids

(e.g. phthalic acid, succinic acid,

alkylsuccinic and alkenyl succinic acids,

  maleic, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, dimer

linoleic acid, malonic acid, alkyl-ma- acids

  lonic, alkenyl malonic acids, etc.) with various al-

  cool (e.g. butyl alcohol, hexyl alcohol, al-

  cool dodecyl, 2-ethylhexyl alcohol, ethylene glycol,

diethylene glycol monoether, propylene glycol, etc.).

  Particular examples of these esters include the adi-

dibutyl paste, di (2-ethylhexyl) sebacate,

di-n-hexyl fumarate, dioctyl sebacate, azide

  diisooctyl laate, diisodecyl azelaate, phta-

  dioctyl late, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting a

mole of sebacic acid with two moles of tetraethylene-

glycol and two moles of 2-ethylhexanoic acid, etc. Esters useful as synthetic oils

also include those formed from monocarbon acids

  xyls from C5 to C12 and polyols and polyol ethers such as

  neopentyl glycol, trimethylolpropane, pentaeryry-

thritol, dipenta-erythritol, tripenta-erythritol, etc.

  Silicon-based oils such as polyal-

  coyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxanes and silicate oils are another useful class of synthetic lubricants (e.g. tetraethyl silicate, tetra-isopropyl silicate, silicate

  tetra- (2-ethylhexyl), tetra- (4-methyl-

  2-ethylhexyl), tetra- (p-tert-butylphenyl) silicate,

  hexa- (4-methyl-2-pentoxy) -disiloxane, poly (methyl) -

siloxanes, poly- (methylphenyl) siloxanes, etc. 7. From-

  very synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g. tricresyl phosphate, trioctyl phosphate, ester

diethyl decylphosphonic acid, etc.), tetra-

polymer hydrofurans, etc.

Unrefined, refined and reraf- oils

  finite, natural or synthetic (as well as mixtures of two or more of any of them) from

  type described above can be used in com-

lubricating positions of the present invention. The oils

  the unrefined ones are those obtained directly from

  taken from a natural or synthetic source without further processing

  purification. For example, a shale oil

obtained directly from distillation operations

retort, a petroleum oil obtained directly by distillation or an ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to unrefined oils, except that they have been further processed in one or more

several purification steps to improve one or more

several properties. Many such techniques of pu-

  are known to those skilled in the art, such as the former

solvent traction, acid or basic extraction, filtration, percolation, etc. Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to oils

  that have already been used in service. These hui-

  the reraffines are also called regenerated or re-treated oils and often are further processed by techniques aimed at the removal of spent additives and

of oil decomposition products.

Generally, the lubricants of this

  invention contain an amount of the composition

lon the present invention sufficient to give them detergent and / or dispersing properties. Normally this amount will be from about 0.01 to about 20%, from pre-

ference from about 0.1 to about 5% of the total weight of the

brifiant.

  The invention also contemplates the use of other

  very additives in combination with the compositions according to the present invention. These additives are, for example,

  detergents and auxiliary dispersants of the product type

ash-free or ashless, cor-

  corrosion and oxidation, pour point reducers-

extreme pressure agents, stabilizing agents

color and anti-foaming agents.

Examples of ash-producing detergents are neutral and basic oil-soluble salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids or acids

  organic phosphorus characterized by at least one bond

  its direct carbon-phosphorus like those prepared by the

  treatment of an olefin polymer (for example polyiso-

  butene having a molecular weight of 1000) with an agent

  phosphorus such as phosphorus trichloride, hep-

phosphorus tasulfide, phosphorus pentasulfide, tri-

phosphorus chloride and sulfur, white phosphorus and

a sulfur halide or phosphorothioic chloride.

  The most commonly used salts of these acids are those of sodium, potassium, lithium, calcium,

magnesium, strontium and barium.

  The ashless detergents and dispersants

liars are so called despite the fact that, depending on its constitution, the dispersant can give on combustion a non-volatile material such as boric oxide or

  phosphorus pentoxide; however, it does not contain

nary no metal and therefore does not give by combustion an ash containing a metal. Many types are known in the art, and any of them

they can be used in lubricants according to the pre-

invention. Examples are:

  (1) Carbohydrate reaction products

cylics (or their derivatives) containing at least approx.

  ron 34 and preferably at least about 54 carbon atoms with nitrogen-containing compounds such as amines, hydroxylated organic compounds such as

  phenols and alcohols and / or inorganic materials

  basic things. Examples of these "carboxy dispersants"

"are described in British Patent No. 1,306,529 and in many US patents including the following: 3,163 3,184 3,215 3,219 3,271 3,272 3,281 3,306 3,311 3,316 3,340 3,341 3,346 3 351 3 381 3 399 3 415 3 422 3 444 3 448 3 448 3 451 3 454 3 467 3 501 3 522 3 541 3 542 3 542 3 567 3 574 3 576 3 630 3 632 3 632 3 697 3 725 Re 26 ( 2) Halide reaction products

  aliphatic or alicyclic molecular weight rela-

high with amines, preferably polyal-

  coylene polyamines. They can be characterized as "amine dispersants" and examples

  are described, for example, in U.S. patents.

following:

3,275,554

3,438,757

3,454 5d5

3,565,804

(3) Alkylphenol reaction products in which the alkyl gourd contains at least about carbon atoms with aldehydes (especially

  formaldehyde) and amines (especially polyalkyl-

  lene polyamines), which can be characterized as é-

so many "Mannich dispersants". The subjects described

  your in U.S. patents following are

examples:

3,413,347 3,725,480

3,697,574 3,726,882

3,725,277

  (4) Products obtained by subjecting the carboxylic dispersants,

  amine or Mannich type with reagents such as u

  rée, thio-urea, carbon sulfide, aldehydes,

  ketones, carboxylic acids, hy-

drocarbyl-succinics, nitriles, epoxides, com-

  installed boron, phosphorus compounds, etc. U.S. patents The following describe examples of such materials:

3,036,003 3,282,955 3,493,520 3,639,242

* 3 087 936 3 312 619 3 502 677 3 649 229

3,200 107 3,366,569 3,513,093 3,649,659

  3,216,936 3,367,943 3,533,945 3,658,836

3,254,025 3,373 111 3,539,633 3,697,574

  3,256,185 3,403 102 3,573,010 3,702,757

  3,278,550 3,442,808 3,579,450 3,703,536

  3,280,234 3,455,831 3,591,598 3,704,308

3,281,428 3,455,832 3,600 372 3,708,522

  (5) Interpolymers of monomers having an oil solubilizing effect such as decyl methacrylate, vinyl decyl oxide and high molecular weight olefins with monomers containing

  polar substituents, for example aminoal acrylates-

coyle or poly (oxyethylene) substituted acrylamides and acrylates. They can be characterized as "polymeric dispersants" and examples are described in US patents. following:

3,329,658 3,666,730

3,449,250 3,687,849

3,519,565 3,702,300

The above mentioned patents are incorporated

  here by reference for their dispersant descriptions

without ash.

  Examples of extreme pressure agents and corrosion and oxidation inhibitors are

  chlorinated aliphatic hydrocarbons such as paraffin

  not chlorinated; organic sulfides and polysulfides such

that benzyl disulfide, bis disulfide (chloro-

benzyl), dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; esters derived from phosphorus comprising mainly

dihydrocarbyl and trihydrocarbyl phosphites

me dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite,

  dicyclohexyl phosphite, pentylphosphite phosphite

nyle, dipentylphenyl phosphite, tri- phosphite

  decyl, distearyl phosphite, dimer phosphite

thyle and naphthyl, oleyl phosphite and 4-pentyl-

  phenyl, polypropylene phosphite (molecular weight

500) -phenyl, diisobutylphenyl phosphite; thio-

metal carbamates, such as zinc dioctyldithiocarbamate and barium heptylphenyl dithiocarbamate; of

  Group II metal phosphorothioates such as dicyclo-

zinc hexylphosphorodithioate, dioctylphosphorodi-

zinc thioate, barium di (heptylphenyl) -phosphorodithioate, cadmium dinonylphosphorodithioate and salt

zinc of a phosphorodithioic acid produced by the reaction

  tion of a phosphorus pentasulfide with an equimo-

  isopropyl alcohol and n-hexyl alcohol.

  Examples of lubricants according to the present invention are given in the following table. All the proportions, except those relating to mineral oil and the products of the examples above, are expressed excluding the mineral oil used as diluent. Parts by weight Lubricant Ingredient Mineral oil Product of Example 1 I It II 9

A B

92.38 96.23

3.30 ---

--- 1.13

---_ _

"14

I "16

Polybutenyl succinic anhydride-alkylene polyamineal alcohol reaction product Polybutenyl aminophenol Basic calcium salt of petroleum sulfonic acid Alkylphenol reaction product,

formaldehyde and 2,5-dimercapto-

1,3,4-thiadiazole Zinc dialkylphosphorodithioate Terpolymer alkyl fumarate-vinyl acetate-vinyl oxide Tert-primary alkyl amine C11_14 Mixture of fatty amides Isobutene sulfide Amine salt of phosphoric acid ester Antifoaming agent silicone 2.50 ___ _-- 2.64 0.66 0.99 0.17 ___ 0.005 2.50 ___ In 0.66

0.006 0.006

--- ---

0.99 n 417

v, I! --- --- ---

--- 0.21 0.21

--- 0.007 0.007

--- 3.15 3.15

--- 0.10 0.10

0.005 0.006 0.006

  It il i If ii If D 92.38 ___ EC 96.00 4.00 4.00 F 96.03 96.03 3.30 ___ 0.50 0.50 ___ 0.50 ri cu CD _ __ Combustible compositions according to this

invention contain a major proportion of a fuel-

normally liquid target, usually a hydrocarbon fuel for metrole distillation such as gasoline for engines as defined by standard ASTM D439-73 or gas oil or fuel oil as defined by standard

  ASTM D396. Normally combustible compositions

  materials comprising materials other than hydrocarbons

res, such as alcohols, ethers, organic compounds

no-nitro, etc. (for example methanol, ethanol, ethyl oxide, methyl and ethyl oxide, nitromethane) are also included in the general scope of the present invention, as well as fuels liquids derived from vegetable or mineral sources such as

  corn, alfalfa, shale and coal. Com-

  normally liquid bustibles which are mixtures of a

  or more hydrocarbon fuels and one or more

  several materials other than hydrocarbons are envisaged

also aged. Examples of such mixtures are

  pairs of petrol and methanol or ethanol and diesel and ether. Gasoline is particularly preferred, that is to say a mixture of hydrocarbons having an ASTM distillation curve ranging from about 600C to 10%

distilled at around 2050C at the point 90% distilled.

  The compositions according to the present invention

are normally added to fuels at a rate of

about 0.0001-0.1% by weight.

  The fuel compositions can also contain other additives which are well known to man.

  art. These additives may include anti-angents

detonants such as lead-tetraalkyl compounds,

  lead scavengers such as haloalka

nes (e.g. ethylene dichloride and ethylene dibromide), agents preventing or modifying deposits such as triaryl phosphates, dyes,

  cetane index improving agents, antioxidants including

  me 2,6-di-teft-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostats, gum inhibitors, metal deactivators, demulsifiers, lubricants for cylinder tops , defrosters, etc. The compositions according to the present invention can be added directly to the fuel or to the lubricant. Preferably, however, they are diluted

  with a normally liquid organic thinner sensitive-

  inert such as mineral oil, naphtha, ben-

  zene, toluene or xylene, to form an additive concentrate. These concentrates usually contain

  at around 90% by weight of the composition according to the pre-

invention and may contain, in addition, one or more

several other additives known in the art or

above.

Claims (17)

  1) A composition comprising a salt or supplement   xed metal or metalloid of at least one aminophenol of the formula (OH) -   c (R) a-r- (NH'2) b in which: Ar is an aromatic radical having no sulfur or amino bonds between its aromatic rings; R is a substantially saturated hydrocarbon radical having at least 30 aliphatic carbon atoms; and a, b and c are each an integer ranging from 1 to three times the number of aromatic rings in Ar. 2) A composition according to claim 1,   characterized in that Ar is a radical based on phe- nyle. 3) A composition according to claim 2, characterized in that Ar is a phenyl radical. 4) A composition according to claim 3, characterized in that a and c are each 1 and b is 1 or 2.) A composition according to claim 4, characterized in that b is 1. 6) A composition according to claim 5, characterized in that R is a hydrocarbon radical   having from 30 to about 750 aliphatic carbon atoms.   7) A composition according to claim 1, characterized in that it is prepared from at most about 1.1 equivalent of metal compound per equivalent of aminophenol.   8) A composition according to claim 1, characterized in that it is prepared from approximately   1/2 to 1 equivalent of metal compound per equivalent of ami nophenol. 9) A composition according to claim 1, ca-   characterized in that it is prepared from sensitive- more than one equivalent of metal compound per equivalent slow aminophenol.   ) A composition according to one of the claims 1 to 6, characterized in that the metal or metallol-   de is at least one of the following: metals from groups IA, IIA or IIB, iron, cobalt, nickel, manganese, silicon, boron, aluminum, tin, molybdenum, tungsten, antimony, lead, copper and bismuth.   11) A composition according to claim 10,   characterized in that R is an alkyl radical having further   about 40 to about 500 carbon atoms. 12) A composition according to claim 11, characterized in that the metal is at least one metal of groups IA, IIA or IIB. 13) A composition according to one of claims   4 to 6, characterized in that R is in position para by relative to the hydroxyl group. 14) A composition according to claim 13, characterized in that the metal or metalloid is at least one of the following: metals from groups IA, IIA or IIB, iron,   cobalt, nickel, manganese, silicon, boron, aluminum, chromium me, tin, molybdenum, tungsten, antimony, lead, copper and bismuth.   ) A composition according to claim 14,   characterized in that R is an alkyl radical having further about 40 to about 500 carbon atoms.   16) A composition according to claim 15, characterized in that the metal is at least one metal of groups IA, IIA or IIB. 17) A process for preparing a composition   as defined in one of claims 1 to 6,   characterized in that at least one nitrophé reacts nol corresponding to the formula (OH) (R) a-Ar- (N02) b   with at least one reactive metal, a reactive metal compound   tif or a metalloid compound and a reducing agent other than elemental sulfur.   18) A method according to claim 17, charac-   terized in that the metal or metalloid is a metal of group IA, IIA or IIB. 19) A method according to claim 18, charac- terized in that R is an alkyl radical having about   40 to about 500 carbon atoms.   ,) An additive concentrate including a diluent   organic normally liquid substantially inert and of   about 20% to about 90% by weight of a composition according to   one of claims 1, 2, 4, 6, 10, 12, 14 and 16 ..   21) A lubricant comprising a major amount re of a lubricating oil and a minor amount of a composition according to one of claims 1, 2, 4, 6, 10, 12, 14 and 16. 22) A combustible composition comprising a major amount of a normally liquid fuel and a minor amount of a composition according to one of the vendications 1, 2, 4, 6, 10, 12, 14 and 16.