FI62555B - BRAENSLE- ELLER SMOERJMEDELSKOMPOSITION - Google Patents

Description

1 “-.---- ... ANNOUNCEMENT

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Patent and registration authorities Amttkan utiijd och utl.skriftm pubticsrmd 30.09.82 (32) (33) (31) Pyri · »/ utuelkeu * - kfftrd priorltat li .10.75 12. Oli. 76 USA (US) 622358, 676172 (71) The Lubrizol Corporation,. P.O. Box 17100, Euclid Station, Cleveland,

Ohio 1 * 1 * 117, USA (72) Richard Michael Lange, Euclid, Ohio, USA (74) Oy Jalo Ant-Wuorinen Ab (54) Fuel or lubricant composition - Bränselleller smörjmedels-composition This the invention relates to additive compositions which can be used in lubricants based on oils having a lubricating viscosity and in normal liquid fuels. In particular, the invention relates to aminophenols having at least one hydrocarbon-based group containing at least about 10 aliphatic carbon atoms.

U.S. Patent 2,197,835 describes the preparation of metal salts of aromatic amines formed by nitration and subsequent reduction of paraffin-substituted hydroxyaromatic hydrocarbons. These metal salts can be added to mineral oils to lower their pour point and increase their viscosity indices.

U.S. Patents 2,502,708 and 2,571,092 describe nitration followed by hydrogenation to produce cardanolamine. This amino-cardanol has been considered a useful antioxidant for mineral oils, fats and crude oil products. Cardanol, also known as anacardine, is said to be 3-pentadecylphenol, 3- (8'-pentadecenyl) -phenol, 3- (81: 11'-pentadecadienyl) -phenol and 3- (8: 11: 14'-pentadecatrienyl) -phenol mixture. The formulas in Patents 2,502,708 and 2,571,092, as well as the chemical literature (cf. Dictionary of Organic Compounds, Vol. 1, Oxford University Press, NY, 1965, p. 229), show that the C 1-6 substituent of cardanol is 6 2 5 5 ύ 2 in the meta-weapon with respect to the hydroxy group.

U.S. Patent 2,859,251 describes the alkylation of ortho, para and metaaminophenols with olefin polymers having 6 to 18 carbon atoms per molecule in the presence of a catalytic complex obtained by mixing hydrogen fluoride with boron trifluoride and an iron group metal fluoride. U.S. Patent 2,859,251 does not mention whether the alkyl groups in the product are attached to a carbon, nitrogen and / or oxygen atom.

It has been known for several decades that the performance of lubricants based on oils with a lubricating viscosity (e.g., oils and greases) and normal liquid fuels can be improved by using additives in them. However, due to the scarcity of raw materials and the ever-increasing costs of equipment, fuel and lubricants, as well as awareness of environmental problems, research to find new, efficient, alternative lubricants and fuels has continued unabated.

It is therefore an object of the present invention to provide novel additive compositions which provide useful and advantageous properties for oil-based lubricants and normal liquid fuels containing said additive compositions.

The invention also relates to novel concentrates and lubricants and fuels containing the aminophenols of this invention.

Other objects of the invention will become apparent from the following description.

This invention relates to aminophenols of the formula

<0H> C

I i (R) ä -Ar - (NH2> b wherein R is a predominantly saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a, b and c are independently an integer from 1 to 3 times the number of aromatics in the group Ar). the number of nuclei, provided that the sum of a, b and c does not exceed the number of unsaturated valencies of the group Ar, and Ar is an aromatic group having 0 to 3 possible substituents selected from lower alkyl, lower alkoxyl, nitro, halogen, or two or more of said a combination of an optional substituent, provided that when Ar is a benzene nucleus having only one hydroxyl and only one R substituent, the R substituent is in the ortho or 362556 para position relative to the hydroxyl substituent.

The term "phenol" is used in this specification in accordance with the general practice in the art to mean hydroxyaromatic compounds having at least one hydroxyl group attached directly to the carbon of the aromatic ring.

Also within the scope of this invention are lubricants based on oils having a lubricating viscosity, normal fuels and additive concentrates containing the aforementioned aminophenols.

The aromatic group Ar may be a simple aromatic nucleus such as a benzene compound, a pyridine nucleus, a thiophene nucleus, a 1,2,3,4-tetrahydronaphthalene nucleus, etc., or a polynuclear aromatic group.

These polynuclear groups may be of the fused type, i.e., those in which at least two aromatic nuclei are fused from two points to another nucleus, such as naphthalene, anthracene, azonaphthalenes, etc. These polynuclear aromatic groups may also be of the bridged type. mono- or polynuclear) by bridging bonds. Such bridging bonds may be simple carbon-carbon bonds, ether bonds, keto bonds, sulfide bonds, polysulfide bonds having 2 to 6 sulfur atoms, sulfinyl bonds, sulfonyl bonds, methylene bonds, alkylene bonds, dl- (lower alkyl) methylene bonds, lower alkyleneoxy, ether alkyleneoxy lower alkylene sulfur bonds, lower alkylene polysulfide bonds having 2 to 6 carbon atoms, amino bonds, polyamino bonds, and combinations of such divalent bridging bonds. In some cases, more than one bridging bond between aromatic rings may be present in the Ar group. For example, a fluorene nucleus has two benzene nuclei bonded by both a methylene bond and a covalent bond. Such a group can be considered to contain three nuclei, but only two of them are aromatic. Normally, Ar contains only carbon atoms in aromatic nuclei per se.

The number of aromatic nuclei in the group Ar, whether fused, bridged, or joined together in both ways, can affect the numerical values a, b, and c in formula I. When Ar contains, for example, a simple aromatic nucleus, a, b, and c are each independently 1-3. When Ar contains two aromatic nuclei, a, b and c may each be an integer from 1 to 6, i.e. from 1 to a number 3 times the number of aromatic 6 2 5 5 ύ 4 nuclei present (e.g. 2 nuclei in naphthalene). When the group Ar has three cores, a, b and c can be an integer from 1 to 9. Thus, when Ar is, for example, a biphenyl group, a, b and c may independently be an integer from 1 to 6. The values of a, b and c are, of course, limited by the fact that their sum cannot be greater than the sum of the unsaturated valencies of the group Ar.

The monocyclic aromatic ring which may form a group Ar can be illustrated by the general formula ar (Q) mf wherein ar represents a monocyclic aromatic ring (e.g. benzene) having 4 to 10 carbon atoms, each group Q independently representing a lower alkyl group, a lower alkoxy group , a nitro group or a halogen atom, and m is 0-3. As used herein and in the claims, "lower" means groups having up to 7 carbon atoms, such as lower alkyl and lower alkoxyl groups. Halogen atoms include fluorine, chlorine, bromine and iodine atoms; halogen atoms are generally fluorine and chlorine atoms.

Examples of such monocyclic Ar groups are the following :, h —— —yK— yS — Me I I ί

H — H — k ^ —H H

B

yV ySj yV.

Me k ^ J H H - 0Pr H — YY — H

- —Λ — Nit

H — H C1 H H

H I ^ ch2 ~ CH2 rrN-cH2-L2

H Η211- H2 H

H2 6 2 5 51> 5, etc., where

Me is methyl, Et is ethyl, Pr is n-propyl and Nit is nitro.

When Ar is a polynuclear aromatic fused as a ring group, it may have the general formula ar "" / "'ar, (Q), where ar, Q and m have the same meaning as above, m1 is 1-4 and ZZZ represents a fusing bond pair that fuses two rings so that two carbon atoms belong to each of two adjacent rings. Specific examples of fused ring aromatic groups Ar are:

B

I I

H H_H

H H

MeO

Nit

H —H H H

B

H MeO -

H -H

H H H

and so on.

When the aromatic group Ar is a bridged polynuclear aromatic group, it can be illustrated by the general formula ar - (_ Lng - ar -4 ^ (Q) mw where w is an integer from 1 to about 20, ar is as defined above, provided that ^ has at least 3 unsaturated (i.e., free) valence in total for all ar groups, Q and m have the same meaning as m 6 62550 above, and each Lng is a bridging bond, which may independently be a simple carbon-carbon bond, an ether bond (e.g., -O- ), ketosides

O

11 (e.g. -C-), sulfide bond (e.g. -S-), polysulfide bond containing 2-6 sulfur bonds (e.g. -S2-g-), sulfinyl bond (e.g. -S (O) -), sulfo- a nyl bond (e.g. -S (O) 2 ') / lower alkylene bond (e.g. -CH 2 -, -CH 2 -CH 2 -, -CH-CH-, etc.), a di- (lower alkyl) methylene bond (e.g.

k ° -CR 2 -), lower alkylene ether bond (e.g. -CH 2 -O-, -CH 2 O-CH 2 -, -CH 2 -CH 2 O-, CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CHOCH 2 CH-, -CH 2 CHOCHCH 2 -, etc.), R 0 - OR 0 OR ° R °

11 M

a lower alkylene ketoside bond (e.g. -CH2C-, -CH2CCH2-), a lower alkylene sulfide bond (e.g. where one or more of the -O- in the lower alkylene ether bond is replaced by an -S atom), a lower alkylene polysulfide bond (e.g. where one or more -O- is -S2-g), an amino bond (e.g. -N-, -N-, -CH_N-, -CH-NCH-, -alk-N-, where alk II 0 * IZI ^ ·

H R

is lower alkylene, etc.), a polyaminosyl bond (e.g., -N (alkN) .-. n, where the 1 'xo unsaturated free N valences contain H atoms or R groups), and combinations of such bridging bonds (such as R 0 is lower alkyl group).

Examples in which Ar is a bridged polynuclear aromatic group include:

H H H H

Λ li. X rt X

H H H H

H H

B

, γΥΥγ H -XyJ- 7 62550

H H

I.? E 1 J1! Hj.

«I 1 \ / 1-10 etc.

All of these Ar groups are generally unsubstituted except R, -OH, and -NH 2 - (and bridging groups).

For reasons of cost, availability, and utility, the group Ar is normally a benzene nucleus, a lower alkylene bridged benzene nucleus, or a naphthalene nucleus. Thus, a typical Ar group is a benzene or naphthalene nucleus having 3-5 unsaturated valencies, so that one or two of these valencies may be saturated with a hydroxyl group, the remaining unsaturated valencies being, if possible, in either the ortho or para position relative to the hydroxyl group. Ar is preferably a benzene nucleus having 3-4 unsaturated valencies, one of which may be saturated with a hydroxyl group and the remaining two or three are either ortho or para to the hydroxyl group.

The aminophenols of this invention contain, directly attached to the aromatic group Ar, a predominantly saturated monovalent hydrocarbon-based group R having at least about 10 aliphatic carbon atoms. This group R may contain up to about 400 aliphatic carbon atoms. More than one such group may be present, but generally no more than two or three such groups are present per aromatic nucleus in the aromatic group Ar. The number "a" denotes the total number of R groups present in formula I. The hydrocarbon-based group generally has at least about 30, and in particular at least about 50 aliphatic carbon atoms and at most about 750 and in particular always about 400, and generally about 300 aliphatic carbon atoms. These R groups are typically alkyl or alkenyl groups.

Hydrocarbon-based groups R are generally prepared from homo- or mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. interpolymers (e.g. copolymers, terpolymers). These olefins are generally 1-mono-olefins. R groups may also be derived from halogenated (e.g., chlorinated or brominated) analogs of such homo- or interpolymers. However, R groups may be derived from other sources, such as monomeric high molecular weight alkenes (e.g. 1-tetraconates) and its chlorinated and hydrochlorinated analogues, aliphatic petroleum fractions, especially paraffin waxes and its cracked and chlorinated, white, analogous those prepared according to the Ziegler-Natta process (e.g. polyethylene fats) and other sources known to those skilled in the art. The unsaturated moiety in the R groups can be reduced or eliminated by hydrogenation according to methods known in the art prior to the nitration step described below.

Here, the phrase "hydrocarbon-based" means a group in which a carbon atom is directly attached to the remainder of the molecule and has, primarily, a hydrocarbon nature. Thus, hydrocarbon-based groups may always contain one non-hydrocarbon radical for every 10 carbon atoms, provided that this radical does not substantially alter the predominant hydrocarbon nature of the group. It will be apparent to those skilled in the art that such radicals include, for example, hydroxyl, halogen (especially chlorine and fluorine), alkoxyl, alkyl mercapto, alkyl sulfoxy, etc. However, these hydrocarbon-based groups R are generally pure hydrocarbyls and do not contain any non-hydrocarbyl radicals.

The hydrocarbon-based groups R are predominantly saturated, i.e., they contain at most one unsaturated carbon-carbon bond for every ten simple carbon-carbon bonds. In general, they contain at most one non-aromatic unsaturated carbon-carbon bond for every 50 carbon-carbon bonds present.

The hydrocarbon-based groups of the aminophenols of this invention are also predominantly aliphatic, i.e., they contain up to one non-aliphatic group (cycloalkyl, cycloalkenyl, or aromatic) having up to 6 carbon atoms for every 10 carbon atoms in Group R. These R however, groups generally contain no more than one such non-aliphatic group for every 50 carbon atoms, and in many cases do not contain any such non-aliphatic groups; i.e., typical R groups are purely aliphatic. These purely aliphatic groups R are preferably alkyl or alkenyl groups.

Examples of predominantly saturated hydrocarbon-based I

The R groups are as follows: i

tetra (propylene) group, I

deca (propylene) group,: tri (isobutylene) group, tetracontanyl group, henpentacontanyl group, a mixture of poly (ethylene / propylene) groups having about 35 to about 70 carbon atoms, oxidatively or mechanically containing about 35 to about 70 carbon atoms a mixture of decomposed poly (ethylene / propylene) groups, a mixture of poly (propylene / 1-hexene) groups having from about 80 to about 150 carbon atoms, a mixture of poly (siobutene) groups having from 20 to 32 carbon atoms, * a mixture of from 50 to 75 carbon atoms on average a mixture of poly (isobutylene) groups.

Typical R groups are derived from homo- or interpolymerized C2-10-1-olefins such as ethylene, propylene, butenes, and mixtures thereof.

A preferred source of R is poly (isobutenes) obtained by polymerizing a C 1-6 refining stream having a butene content of 35-75% by weight and an isobutene content of 15-60% by weight, typically 30-60% by weight of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. acid. These polybutenes contain mainly (more than 80% of the total number of repeating units) repeating isobutylene units with the formula 62555 10 CH-

- CH0-- C

2 I

CH3

Coupling of the hydrocarbon-based group R to the aromatic group Ar of the amino-phenols of the invention can be accomplished by a number of methods well known to those skilled in the art. One particularly suitable technique is the Friedel-Crafts reaction, in which an olefin (e.g., an olefin-bonded polymer) or a halogenated or hydrohalogenated analog thereof is "reacted with a phenol. This reaction takes place over a Lewis acid catalyst (e.g., boron trifluoride and its ether). complexes with phenols, hydrogen fluoride, etc. in the presence of aluminum chloride, aluminum bromide, zinc dichloride, etc. Methods and conditions for carrying out such reactions are well known to those skilled in the art, cf., for example, Alkylation of Phenols, Kirk-Othmer Encyclopedia of Chemical Technology ", Second Edition, Vol. 1, pp. 894-895, Inter-science Publishers, John Wiley and Company, NY, 1963. Other suitable and simple methods for attaching a hydrocarbon-based group R to an aromatic group Ar are well known to those skilled in the art.

As shown in formula I, the aminophenols of this invention contain at least one of the following substituents: a hydroxyl group, an R group as defined above, and a primary amino group, -NH 2. Each of the above groups is attached to a carbon atom that is part of the aromatic nucleus of the Ar group. However, they need not be attached to the same aromatic ring if there is more than one aromatic ring in the Ar group.

According to a preferred embodiment, the aminophenols of this invention contain one of the above-mentioned substituents but only one aromatic ring, preferably a benzene ring. This preferred class of aminophenols can be illustrated by the formula

R '- I

(R "MZ

11,62555 wherein the R 'group is a hydrocarbon-based group having from about 30 to about 400 aliphatic carbon atoms in the ortho or para position relative to the hydroxyl group, R' '' is a lower alkyl, lower alkoxyl, nitro group or halogen atom , and z is 0 or 1. In general, z is 0 and R 'is a predominantly saturated, purely aliphatic group. It is often an alkyl or alkenyl group in the para position with respect to the OH substituent.

Another class of aminophenols of the invention are compounds of the formula OH 'Λ R -f χ - (ΝΗ2) ι_2 (R') z wherein R is a predominantly saturated hydrocarbyl substituent having an average of about 30 to about 750 aliphatic carbon atoms; R 'is a lower alkyl, lower alkoxy, nitro or halogen substituent, and z is 0 or 1, provided that R is in the ortho or para position relative to the hydroxy group.

According to an even more preferred embodiment of the invention, the amino phenols have the formula OH '> ™ 2 -1

V

R "wherein R" is derived from homopolymerized or interpolymerized C 2-1 olefins and contains an average of about 30 to about 300 aliphatic carbon atoms, and R "'and z have the same meaning as above.

R "is generally derived from ethylene, propylene, butylene, or mixtures thereof. Typically, it is derived from polymerized iso-butene. The group R" generally contains at least about 50 aliphatic carbon atoms and z is 0.

Another class of aminophenols of the invention are compounds of formula 12,62555

OH

¥ 0-1 ^ 1 / NH2

(R) z-R

V

R

wherein R is derived from homopolymerized or interpolymerized C 2-4 olefins and contains an average of about 30 to about 750 aliphatic carbon atoms, R 'is lower alkyl, lower alkoxyl, nitro or halogen, and z is 0 or 1, provided that when present only one amino group is ortho to the phenolic hydroxy group, the group R *, if present, may be ortho to said hydroxyl group. In this case, R often contains on average at least 50 aliphatic carbon atoms and is derived from homo- or interpolymers of mixtures of ethylene, propylene, butenes and the like. Typical R groups are derived from polymerized isobutene.

The aminophenols of the invention can be prepared by a number of different synthetic methods. These methods may vary depending on the type of reaction used and the relative order. For example, an aromatic hydrocarbon such as benzene can be alkylated with an alkylating agent such as a polymeric olefin to form an alkylated aromatic intermediate. This intermediate can then be nitrated, for example to prepare a polynitro intermediate. The polynitro intermediate, in turn, can be reduced to the diamine, which can then be diazotized and reacted with water to convert the amino groups to a hydroxyl group and produce the desired aminophenol. Alternatively, one nitro group of the polynitro intermediate can be converted to a hydroxyl group by melting with a base to produce a hydroxy-nitroalkylated aromatic compound, which can then be reduced to produce the desired aminophenol.

Another useful method for preparing the aminophenols of the invention involves alkylating a phenol with an olefinic alkylating agent to an alkylated phenol. This alkylated phenol can then be nitrated to the intermediate nitrophenyl, which can be converted to the desired aminophenol by reducing at least 13,62555 parts of the nitro group to amino groups.

Methods for alkylating phenols are well known to those skilled in the art, cf. for example, the aforementioned Kirk-Othmer "Encyclopedia of Chemical Technology". Methods for nitrating phenols are also known, cf. for example, Kirk-Othmer, "Encyclopedia of Chemical Technology," Second Edition, Vol. 13, an article entitled "Nitrophenols", p. 888 et seq., And "Aromatic Substitution; Nitration and Halogenation", P.B. De La Mare and J.H. Ridd, N.Y., Academic Press, 1959; "Nitration and Aromatic Reactivity", J.G. Hogget, London, Cambridge University Press, 1961; and "The Chemistry of the Nitro and Nitroso Groups," Henry Feuer, Editor, Interscience Publishers, N.Y., 1969.

Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid with acids such as sulfuric acid or boron trifluoride, nitrogen tetroxide, nitronium tetrafluoroborates and acyl nitrates. A suitable nitration reagent is generally nitric acid at a concentration of, for example, about 30-90%, generally about 60-90%. The reaction can be aided by the use of predominantly inert liquid diluents and solvents, such as acetic or butyric acid, which enhance the contact between the reagents.

Conditions and concentrations for nitration of hydroxyaromatic compounds are also well known in the art. For example, the reaction can be carried out at a temperature of about -15 to about 150 ° C.

In general, the nitration is suitably performed at about 25 to about 75 ° C.

Depending on the particular nitrating agent used, about 0.5 to 4 moles of nitrating agent per mole of aromatic core in the nitroxy-aromatic intermediate is generally used. If the Ar group has more than one aromatic nucleus, the amount of nitrating agent can be increased corresponding to the number of such nuclei present. For example, one mole of a naphthalene-based aromatic intermediate in this invention corresponds to two "monocyclic" aromatic nuclei, so that in this case about 1 to 4 moles of nitrating agent are generally used. When nitric acid is used as the nitrating agent, it is generally used in an amount of about 1.0 to about 3.0 moles, per mole of aromatic nucleus. It is always possible to use an excess of about 5 molar nitrating agent (per "monocyclic" aromatic core) when it is desired to promote or carry out the reaction rapidly.

The nitration of the hydroxy-aromatic intermediate generally takes 0.25 to 24 hours, although it may be appropriate to react the nitration mixture for longer periods of time, such as 96 hours.

14 62556

The reduction of aromatic nitro compounds to the corresponding amines is also known, cf. for example, the article "Amination by Reduction", Kirk-Othmer's "Encyclopedia of Chemical Technology", second edition, Vol. 2, pp. 76-99. Such reductions can generally be carried out, for example, with hydrogen, carbon monoxide or hydrazine (or mixtures thereof) in the presence of metal catalysts such as palladium, platinum and its oxides, nickel, copper chromite, etc. Co-catalysts such as alkali or alkaline earth metal hydroxides or amines (including aminophenols) can also be used in these catalyzed reductions.

The reduction can also be performed using reducing metals in the presence of acids such as hydrochloric acid. Typical reducing metals include zinc, iron and tin; salts of these metals can also be used.

Nitro groups can also be reduced by the Zinin reaction, cf. "Organic Reaction," Vol. 20, John Wily & Sons, N.Y., 1973, pp. 455 et seq. The zinin reaction generally involves the reduction of a nitro group with divalent negative sulfur compounds such as alkali metal sulfides, polysulfides and hydrosulfides.

Nitro groups can be reduced electrolytically cf. for example, the aforementioned article "Amination by Reduction."

Ammonophenols are typically obtained by reducing nitrophenols with hydrogen in the presence of a metal catalyst such as one of the aforementioned catalysts. This reduction is generally performed at a temperature of about 15-250 ° C, typically about 50-150 ° C with a hydrogen pressure of about 1-140 bar (0-2000 psig), typically about 4.5-18 bar (50-250 psig). ). The reduction reaction time is usually about 0.5 to 50 hours. The reactions can be promoted by using mainly inert liquid diluents and solvents such as ethanol, cyclohexane, etc. The aminophenol product is obtained by well-known methods such as distillation, filtration, extraction, etc.

The reduction is continued until at least about 50%, generally about 80% of the nitro group number of the nitro medium mixture has been converted to amino groups. The above typical process for the preparation of aminophenols can be summarized as follows: (I) nitration of at least one compound of formula (OH) with at least one nitrating agent | c m - Ar '15 62556 wherein R is a predominantly saturated hydrocarbon-based group having at least 10 aliphatic carbon atoms; a and c are independently an integer from 1 to 3 times the number of aromatic nuclei in the group Ar, provided that the sum of the numbers a, b and c does not exceed the number of unsaturated valences in the group Ar '; and Ar 'is an aromatic group having 0 to 3 possible substituents such as lower alkyl, lower alkoxyl, nitro and halogen or a combination of two or more such possible substituents, provided that (a) Ar' contains at least one hydrogen atom directly attached to such carbon atom which forms part of an aromatic nucleus, and Cb) when Ar 'is benzene having only one hydroxyl and only one R substituent, the R substituent is ortho or para to said hydroxyl substituent, a first nitro intermediate-containing to form a reaction mixture and (II) reducing at least about 50% of the nitro groups in said first reaction mixture to amino groups.

This generally means reducing at least about 50% of the nitro groups to amino groups in the compound or mixture of compounds of formula <OH) c

I C

(R) --- Ar-- (NO 2) b wherein R is a predominantly saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a, b and c are each independently an integer from 1 to 3 times the number of aromatic nuclei present in the Ar group, provided that the sum of the numbers a, b and c does not exceed the number of unsaturated valencies in the Ar group; and Ar is an aromatic group having 0 to 3 possible substituents such as lower alkyl, lower alkoxyl, nitro, halogen, or a combination of two or more such possible substituents; provided that when Ar is a benzene nucleus having only one hydroxyl and only one R substituent, the R substituent is in the ortho or para position relative to said hydroxyl substituent.

Another typical process for the preparation of certain aminophenols of the invention comprises (I) nitrating at least one compound of formula 62555 with at least one nitrating agent.

OH

Λ R - j ---— (R ') z wherein R is a predominantly saturated hydrocarbyl having from about 30 to about 750 aliphatic carbon atoms, R' is a lower alkyl, lower alkoxyl, nitro or halogen substituent, z is 0 or 1, to prepare a reaction mixture containing the first nitro intermediate, and (II) reducing at least about 50% of the nitro groups in the first reaction mixture to amino groups. The nitrating agent is usually nitric acid and the reduction is performed with hydrogen in the presence of a metal hydrogenation catalyst. The R group is in the ortho or para position relative to the phenolic hydroxyl group.

The following examples illustrate the invention. All parts and percentages are by weight, and all temperatures are in degrees Celsius (° C) in these examples and elsewhere in the specification, unless otherwise indicated.

Example IA:

To a mixture of 361.2 parts of tetrapropenyl-substituted phenol and 270.9 parts of glacial acetic acid is added, at 7-17 °, a mixture of 90.3 parts of nitric acid (70-71% HNO 2) and 90.3 parts of glacial acetic acid. The addition is carried out for 1.5 hours while the reaction vessel is cooled externally to maintain its temperature at 7-17 °. The cooling bath is removed and the reaction mixture is stirred for 2 hours at room temperature. The reaction mixture is then distilled at 134 ° / 35 torr and filtered to give the desired nitro intermediate as a filtrate with a nitrogen content of 4.65%.

Example IB:

A mixture of 150 parts of product IA and 50 parts of ethanol is added to the autoclave. This mixture is degassed by purging with nitrogen and 0.75 parts of palladium-on-carbon catalyst are added. The autoclave is evacuated and charged with nitrogen several times and then the hydrogen pressure is raised to 100 psig. The reaction mixture is maintained at 95-100 ° for 2.5 hours with a hydrogen pressure of about 7.9-2.4 bar (100-20 psig). When the hydrogen pressure drops below about 3.1 bar (30 psig), it is adjusted back to about 7.9 bar (100 psig). The reaction is continued for 20.5 hours, after which the autoclave is opened and a further 0.5 part of palladium-on-carbon catalyst is added. repeated

6 2 5 5 S

After 17 hours of nitrogen purge (3 times), the hydrogen pressure in the autoclave is raised again to about 7.9 bar (100 psig) and the reaction is continued for another 16.5 hours. A total of 1.63 moles of hydrogen is fed to the autoclave. The reaction mixture is filtered and distilled to 130 ° / 16 torr. Repeated filtration gives a product with a nitrogen content of 4.78%.

Example 2A;

To a mixture of 3685 parts of polyisobutylene-substituted phenol (in which the polyisobutylene substituent contains 22 to 25 carbon atoms) and 1400 parts of textile spirit is added 790 parts of nitric acid (70%). I

The temperature of the reaction mixture is kept below 50 °. Stir about 0.7; hours, after which the reaction mixture is poured into 5000 parts of ice and stored for 16 hours. The separating organic layer is washed twice with water and then combined with 1000 parts of benzene. This solution is distilled to 170 ° and the residue is filtered to give the desired intermediate I with a nitrogen content of 2.41% and a viscosity; ti at 99 ° 150.8 SUS.

Example 2B:

A mixture of 130 parts of product 2A, 130 parts of ethanol and 0.2 parts of platinum oxide (PtCl 2) is charged to a hydrogenation bomb. The bomb is flushed several times with hydrogen and then charged with about 4.7 barbs (54 psig) of hydrogen. The bomb is rocked for 24 hours and reloaded at 70 psig with hydrogen. The rocking is continued for another 98 hours. Distillation of the resulting reaction mixture to 145 ° / 760 torr gives the desired product.

Example 2C:,

A mixture of 420 parts of product 2A, 326 parts of ethanol and 12 parts of a commercial nickel-diatomaceous earth catalyst is charged to a suitably sized 7 size hydrogenation bomb. The pressure in the process is raised to about 103 bar (1480 psig) with hydrogen and shaken for 5.25 hours. The reaction mixture obtained is distilled at 65 ° / 30 torr to give a product with a nitrogen content of 2.62%.

Example 2D:

A mixture of 105 parts of product 2A, 303 parts of cyclohexane and 4 parts of commercial Raney nickel catalyst is charged to a suitably sized hydrogenation bomb. The pressure of the pony is raised to about 70 bar (1000 psig) with hydrogen and shaken at about 50 ° for 16 hours. The pressure of the bomb is raised again to about 77 bar (1100 psig) and shaken for another 24 hours. The bomb is opened and the reaction mixture is filtered and re-charged to the bomb along with 4 parts of Raney nickel catalyst. The bomb

6 2 5 5 S

The pressure is raised to n, 77 bar (1100 psig) and shaken for 24 hours. The resulting reaction mixture is distilled at 95 ° / 28 torr to give a product with a hydroxyl content of 5.24% and a nitrogen content of 2.25%. Example 3A:

An alkylated phenol is prepared by reacting the phenol with a polyisobutylene having an average molecular weight of about 1000 (vapor phase osmometry) in the presence of a boron trifluoride-phenol complex catalyst. The product thus formed is first distilled to 230 ° / 760 torr (vapor temperature) and then to a vapor temperature of 205 ° / 50 torr to give purified alkylated phenol.

To a mixture of 265 parts of purified alkylphenol, 176 parts of mixed oil and 42 parts of solvent gasoline having a boiling point of about 20 ° is slowly added to a mixture of 18.4 parts of concentrated nitric acid (69-70%) and 35 parts of water. The reaction mixture is stirred for 3 hours at about 30-45 °, distilled to 120 ° / 20 torr and filtered to give an oily solution of the desired nitrophenol intermediate.

Example 3B:

A mixture of 1500 parts of the product solution of Example 3A, 642 parts of isopropanol and 7.5 parts of nickel-diatomaceous earth catalyst is charged to the autoclave under a nitrogen atmosphere. Nitrogen is blown into it and evacuated three times, after which the pressure in the autoclave is raised to n, 7.9 bar (100 psig) with hydrogen and stirring is started. The reaction mixture is maintained at 96 ° for a total of 14.5 hours while being fed a total of 1.66 moles of hydrogen. Nitrogen is blown in and evacuated three times, after which the reaction mixture is filtered and the filtrate is distilled to 120 ° / 18 torr. Filtration gives the desired product as a solution containing 0.54% nitrogen.

Example 4A:

To a mixture of 400 parts of polyisobutylene-substituted phenol (in which the polyisobutylene substituent contains about 100 carbon atoms), 125 parts of textile spirit and 266 parts of diluent mineral oil at 28 ° are slowly added 22.83 parts of nitric acid (70%) in 50 parts of water 0, Within 33 hours. The mixture is stirred at 28-34 ° for 2 hours and distilled at 158 ° / 30 torr, filtered to give an oil solution (40%) of the desired intermediate with a nitrogen content of 0.88%.

Example 4B:

A mixture of 93 parts of the product solution of Example 4A and 93 parts of a mixture of toluene and isopropanol (50/50 by weight) is charged to a suitably sized hydrogenation vessel. The mixture is degassed and nitrogen is blown into it; 0.31 parts of commercial is added

G 2 5 5 S

19 platinum oxide catalysts (86.4% PtCl 2) - The pressure in the reaction vessel is raised to about 4.9 bar (57 psig) and maintained at 50-60 ° for 21 hours. A total of 0.6 moles of hydrogen is fed to the reaction vessel. The reaction mixture is then filtered and the filtrate is distilled to give the desired product as an oil solution containing 0.44% nitrogen.

Example 5A:

A mixture of 2160 parts of the polyisobutylene-substituted phenol of Example 4A and 1440 parts of mineral oil as diluent is heated to 60 °. 25 parts of paraformeldehyde are then added to the mixture, followed by 15 parts of aqueous hydrochloric acid. The mixture is heated at 115 ° for 1 hour. After 16 hours at room temperature, the reaction mixture is heated at 160 ° for one hour while removing 20 parts of distillate. The reaction mixture is distilled at 160 ° / 15 torr to give an oily solution of the desired methylene-linked polyisobutylene-substituted phenol.

Example 5B: To 2406 parts of the oil solution described in Example 5A and 600 parts of textile spirit, 90 parts of nitric acid (70%) are added over 1.5 hours. The reaction mixture is stirred for 1.5 hours, kept at room temperature for 63 hours and then heated at 90 ° for 8 hours. Distill to 160 ° / 18 torr to give an oil solution of the desired nitrated intermediate containing 0.79% nitrogen.

Example 5C;

A mixture of 800 parts of the oil solution of Example 5B and 720 parts of a toluene / isopropanol mixture (60/40 by weight) is charged to the autoclave. Rinse with nitrogen, then add 4 parts of nickel-diatomaceous earth catalyst. The nitrogen purges are repeated three times and the autoclave pressure is raised with hydrogen to about 6.1 bar (60 psig) at 25 °. The reaction temperature is slowly raised to 96 ° and the pressure is maintained at n, 7.9 bar (100 psig) for 5.5 hours. The autoclave is then opened and a further 4 parts by weight of nickel-diatomaceous earth catalyst are added. The pressure in the autoclave is raised again to about 7.9 bar of hydrogen and kept at 96 ° / 7.9 bar for 6 hours. The autoclave is cooled and reopened; an additional 0.8 parts of platinum oxide catalyst is added. The autoclave pressure is then raised again to 7.2 bar (90 psig) with hydrogen · and maintained at this pressure for a further 8 hours. The reaction mixture is filtered and distilled to 150 ° / 18 torr to give an oil solution of the product with a nitrogen content of 0.41%.

Example 6A:

A mixture of 1962 parts of the polyisobutylene-6 20 62555 ni-substituted phenol of Example 3A, 49.5 parts of paraformaldehyde, 15 parts of aqueous hydrochloric acid and 1372 parts of mineral oil diluent is heated at 115 ° for 7 hours. The reaction temperature is then raised to 160-165 ° and maintained at this temperature for a further 7 hours. An additional 400 parts of textile spirit is then added to the mixture and cooled to 30 °. 136.95 parts of nitric acid (70%) in 140 parts of water are then slowly added. The reaction mixture is stirred for 1.5 hours at 30-35 ° and then distilled to 170 ° / 28 torr to give an oil solution of the intermediate which is clarified by filtration. Example 6B: 96 parts of the oil solution described in Example 6A and 96 parts of a toluene / isopropanol mixture (50/50 by weight) are charged as appropriate. hydrogenation vessel. Rinse with nitrogen, then add 0.32 parts of platinum oxide catalyst. The reaction vessel is flushed again after which its pressure is raised to about 12 bar (157 psig) at 25 ° with hydrogen. The hydrogen pressure is maintained at about 4.9-4.5 bar (57-50 psig) for 60 hours while heating the reaction mixture at 50-60 °. The resulting reaction mixture is filtered and distilled to give an oil solution of the product with a nitrogen content of 0.353%.

Example 7A:

To a mixture of 654 parts of the polyisobutylene-substituted phenol of Example 3A and 654 parts of isobutyric acid at 27-31 ° is added 90 parts of 16 molar nitric acid over 0.5 hours. The reaction mixture is kept at 50 ° for 3 hours and then stored at room temperature for 63 hours. Distill to 160 ° / 26 torr and filter to give the desired nitro intermediate with a nitrogen content of 1.8%.

Example 7B:

The nitro product of Example 7A is hydrogenated using a nickel-silicon ore catalyst essentially as described in Example 3B.

Example 8A:

A mixture of 4578 parts of the polyisobutylene-substituted phenol of Example 3A, 3052 parts of a mineral oil diluent and 725 parts of a textile spirit is heated to 60 ° until homogeneous.

After cooling to 30 °, 319.5 parts of 16 molar nitric acid in 600 parts of water are added to the mixture. Cool to keep the temperature below 40 °. The reaction mixture is stirred for a further 2 hours, after which 3710 parts of the mixture are transferred to another reaction vessel. These 3710 parts are further treated with 127.82 parts of 16 molar <41

6 2 5 5 S

21 nitric acid in 130 parts of water at 25-30 °. The reaction mixture is stirred for 1.5 hours and then distilled to 220 ° / 30 torr. Filtration gives an oil solution of the intermediate.

Example 8B:

The oil solution of the product obtained according to Example 8A is hydrogenated using a platinum oxide catalyst mainly as described in Example 2B to prepare diaminophenol.

Example 9:

A mixture of 543 parts of dinitro-C25-alkylated phenol (prepared mainly as described in Example 8B), 543 parts of isopropanol and 200 parts of toluene are treated at 19 ° with a total of 42 parts of gaseous ammonia over 0.75 hours. The reaction mixture is then treated with 147 parts of gaseous hydrogen sulfide. Both ammonia and sulfur carbon treatment are performed by feeding the gas below the surface of the stirred mixture. The ammonia treatment is repeated using 82 parts of gaseous ammonia and then finally treated with 102 parts of carbon disulphide. Distillation of the reaction mixture at 40 ° / 60 torr gives a residue which is combined with 161 parts of diluent oil and distilled again at 70 ° / 18 torr. An additional 161 parts of oil diluent and 35 parts of filter aid are added; filtration of this mixture gives a viscous filtrate which is a 40% solution of diaminophenol.

The nitrations of Examples 10-16 are filtered essentially as described in Example IA using the hydroxy aromatic compounds and amounts of nitric acid listed in Table A. In these examples, the reduction of nitro intermediates is performed using the technique mentioned in the examples in Table A.

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Example 17A:

To a mixture of 1056 parts of tetrapropyl-substituted phenol and 792 parts of acetic acid cooled to -9 ° is added a mixture of 282 parts of concentrated nitric acid and 264 parts of acetic acid. The reaction mixture is stirred at 8-27 ° for 5 hours; external cooling is used to maintain the reaction temperature in this range. The reaction mixture is distilled at 132 ° / 36 torr and the residue is filtered to give the desired nitro intermediate.

Example 17B:

To a mixture of 680 parts of the intermediate described in Example 17A, 340 parts of denatured ethanol and 100 parts of water is rapidly added 423 parts of commercial sodium sulfide. A cooling bath is used to keep the reaction temperature below about 65 °. Stir for about 1 hour, then reflux the reaction mixture for 4 hours. Carbon dioxide is then blown into the reaction mixture at 45-30 ° for 3 hours; add 500 parts of solvent gasoline to the precipitate and stir for 16 hours. 500 parts of toluene are added, after which the reaction mixture is extracted with 500 parts of water. This extraction is repeated 4 times and the combined aqueous extracts are back-extracted with a mixture of solvent-petrol and toluene. The organic extracts are combined and distilled to give a residue which is combined with 409 parts of a mixed oil. The combined mixture is then distilled at 105 ° / 15 torr to give an oily solution of the desired aminophenol.

As mentioned above, the amino-phenols of this invention are useful additives in the preparation of lubricant compositions in which they act primarily as detergents and dispersants. They are particularly useful in cases where the oil is exposed to high temperatures or repeated stresses, such as in intermittent engines. ! The lubricating oil compositions of this invention are based on! natural and synthetic lubricating oils and their mixtures. Such lubricants include crankcase lubricants for spark and 1 compression ignition internal combustion engines, such as automotive and j

for truck engines, boat and locomotive diesel engines, etc. Also automatic transmission fluids, transmission shaft, I

= ‘^ Gearbox * -v metalworking lubricants, hydraulic fluids and others; lubricants and greases can be improved by adding the aminophenols of the invention.

Natural oils include animal and vegetable oils (for example, castor oil, r - «'lard oil) and mineral lubricating oils, such as liquid petroleum oils • r 24 6255ii and solvent - treated or acid - treated paraffinic, naphthenic or mixed paraffinic - naphthenic oils. Useful base oils also include oils having a lubricating viscosity derived from coal or shale.

Synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.); poly (1-hexenes), poly (1-octenes), poly (1-decenes), etc., and mixtures thereof; alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di- (2-ethylhexyl) benzenes, etc.); polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues, and the like.

Another class of known synthetic lubricating oils are alkylene oxide homopolymers and interpolymers and their derivatives in which the terminal hydroxyl groups have been modified by esterification, etherification with ethylene ethylene ethylene ethylene ethylene (ethylene oxide and propylene oxide). having an average molecular weight of 1000, polyethylene glycol diphenyl ether having a molecular weight of 500 to 1000, polypropylene diethyl ether having a molecular weight of 1000 to 1500, etc.) or mono- and polycarboxylic esters thereof, for example acetic acid esters, mixed C8-C8 fatty acid esters or the C 1-8 oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils are dicarbacacylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids, alkenylsuccinic acids, maleic acid, azealic acid, lactic acid, capric acid, sebacic acid, fumaric acid, fumaric acid, adipic acid, adipic acid, with alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Examples of such esters are dibutyl adi%. paate., di- (2-ethylhexyl) sebacate, di-n-hexyl fumarate, di-octyl sebacate, di-isooctyl azelate, diisodecyl acelate, di-octyl phthalate, di-Decyl phthalate, di-eicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, complex, m ester, - obtained by reacting 1 mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those prepared from C5-C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylololpropane, pentaerythritol, dipentaerythritol, tri-pentaerythritol.

Silicone-based oils such as polyalkyl, polyaryl, polyalkoxy or polyaryloxy-siloxane oils and silicate oils form another useful class of synthetic lubricants (e.g. tetraethylsilicate, tetraisopropylsilicate, tetra- (2-ethylhexyl) silicate) silicate silicate, tetra- (p-tert-butylphenyl) silicate, hexyl- (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxanes, poly (methylphenyl) siloxanes, etc. Other synthetic lubricants include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymeric tetrahydrofurans, and the like.

Unrefined, refined and refined oils, either natural or synthetic, of the type described above (as well as mixtures of two or more of these) may be used in the lubricant compositions of the invention. Unrefined oils are obtained directly from a natural or synthetic source without further purification. For example, the unrefined oil may be shale oil obtained directly from distillation processes, petroleum oil obtained directly from pre-distillation, or ester oil obtained directly from the esterification process and used without further processing. Refined oils correspond to unrefined oils except that they have been further processed in one or more refining steps to improve one or more properties. Such purification procedures are known to those skilled in the art and include, for example, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. The refined oils are obtained according to the methods used for the preparation of refined oils using refined oils once used as starting material. Such oils, also known as regenerated oils, are also known as regenerated oils and are often further treated to remove used additives and oil decomposition products.

Generally, about 0.05-30, generally about 0 * 1-15 parts (by weight) "of at least one aminophenol of the present invention is dissolved or dispersed in 100 parts of an oil to produce a satisfactory lubricant. Other additives may be used in accordance with the invention. together with the composition of the present invention Such additives include, for example, additional detergents and dispersants, which may be of the ash-forming or non-ash-type type, antioxidants, pour point depressants, high-pressure agents, color stabilizers and antifoams.

The aminophenols according to the invention can also be used in fuels in which they act as detergent dispersants, antioxidants and corrosion inhibitors.

The fuel compositions of this invention generally contain predominantly normal liquid fuel, such as hydrocarbonaceous petroleum distillate (e.g., gasoline according to ASTM D-439-73 and diesel and fuel oil according to ASTM D 396). Also within the scope of this invention are normal liquid fuel compositions containing non-hydrocarbonaceous substances such as alcohols, ethers, organonitro compounds and the like (e.g. methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) as liquid fuels obtained or from mineral sources such as corn, alpha-alpha, shale and coal.

Also within the scope of the invention are normal liquid fuels (which are mixtures of one or more hydrocarbon fuels with one or more non-hydrocarbon substances. Examples of such mixtures are mixtures of petrol and ethanol, diesel oil and ether, petrol and nitromethane, etc. A particularly preferred fuel is petrol). that is, a mixture of hydrocarbons having an ASTM boiling point of 60 ° at a distillation point of 10% to about 205 ° at a distillation point of 90%.

These fuel compositions generally contain an amount of at least one aminophenol of this invention (sufficient to impart antioxidant and / or dispersing and detergent properties to the fuel; this amount is generally from about 1 to about 10,000, preferably from 4 to 1,000 parts by weight of reaction product 1. million parts by weight of fuel The preferred gasoline-based fuel compositions generally have excellent engine oil sludge dispersant and detergent properties and are resistant to oxidation.

The fuel compositions of this invention may contain, in addition to the compositions of the invention, other additives well known to those skilled in the art. These may be anti-knock agents such as tetraalkyl-lead compounds, lead scavengers such as haloalkanes (e.g. ethylene dichloride and ethylene dibromide), anti-fouling agents or modifiers such as triaryl phosphates, colorants, cetane agents such as 2,6-di-tert-butyl-4-methylphenol, anti-corrosion agents such as alkylated succinic acids and anhydride. bacteriostatic agents, resin inhibitors, metalles; activators, de-emulsifiers, cylinder head lubricants | substances, anti-freeze agents and the like. '

Certain preferred fuel compositions of the invention combine the aforementioned compositions of the invention: with other non-ash dispersants in gasoline. Such non-ash dispersants are! preferably esters of mono- or polyols with a high molecular weight mono- or> polycarboxylic acid acylating agent containing at least> 30 carbon atoms in the acyl group. Such esters are expert; well known, cf. e.g., FR patent 1,396,645, GB-pa-! exams 981,850 and 1,055,337 and U.S. Patents 3,255,108; 3,311,558; : 3 331 776; 3,346,354; 3,522,179; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428; 3,708,522; and GB Patent 1,306,529. These patents are included in this specification because they disclose suitable esters and methods for their preparation. In general, the weight ratio of the compositions of the invention to the above ash-free dispersants is from about 0.1 to about 10.0, preferably from about 1 to about 10 parts per part of the dispersant of the composition of the invention.

According to another embodiment of the invention, the aminophenols according to the invention can be combined with Mannich condensate products obtained from substituted phenols, aldehydes, polyamines and aminopyridines for the preparation of lubricating and / or fuel additives. Such condensation products are described in U.S. Patents 3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277.

The aminophenols of this invention may be added directly to the fuel or lubricating oil to prepare the fuel or lubricating compositions of the invention or may be diluted with at least one substantially inert normally liquid organic solvent / diluent such as mineral oil, xylcene or normal liquid fuel as above.

Claims (36)

62555 28 to form an additive preparation which is then added to the fuel or lubricating oil in an amount sufficient to prepare the fuel and / or lubricant composition of the invention. These concentrates generally contain from about 30% to about 90% of the composition of the invention and may further contain any of the above-mentioned common additives, in particular the above-mentioned non-ash dispersants in the above-mentioned ratios. The remainder of the concentrate consists of solvent / diluent. j A fuel or lubricant composition having more than normal liquid fuel or lubricating oil of lubricating viscosity and less aminophenol, characterized in that the aminophenol used as an additive has the formula (0H) c I ° <R> i-Ar- (NH2> b where R is a predominantly saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms, a, b and c each independently being an integer from 1 to 3 times the number of aromatic nuclei in group Ar, provided that the sum of numbers a, b and c does not exceed the number of unsaturated valencies in group Ar and Ar is an aromatic group having 0 to 3 possible substituents selected from lower alkyl, lower alkoxyl, nitro, halogen, or a combination of two or more of said possible substituents, provided that when Ar is a benzene nucleus having only one hydroxyl and only one R substituent, the R substituent being in the ortho or para position relative to the hydroxyl substituent. Composition according to Claim 1, characterized in that R contains on average at most about 750 aliphatic carbon atoms. Composition according to Claim 2, characterized in that R is a purely hydrocarbyl substituent. Composition according to Claim 3, characterized in that R is alkyl or alkenyl. Composition according to Claim 1, characterized in that R is a substituent (which contains on average at least about 30 aliphatic carbon atoms and is prepared from homopolymerized or κμ <, <. 29 52556 interpolymerized C 2 -C 10 olefins. Composition according to Claim 5, characterized in that the C 2-6 olefins are C 2-6 olefins or mixtures thereof. Composition according to Claim 6, characterized in that the 1-olefin is ethylene, propylene, butylene or a mixture thereof. Composition according to Claim 1, characterized in that Ar contains at least two bridged and / or fused polynuclear aromatic nuclei. Composition according to Claim 1, characterized in that Ar is a naphthalene core. Composition according to Claim 8, characterized in that the aromatic ring Ar corresponds to the formula ar - (- Lng-ar-hr- (Q) „. 3. mw wherein ar is a simple ring and a fused ring core having 4-10 carbon atoms, provided that it has at least three unsaturated valencies in total in all ar groups, w is an integer from 1 to 20 and each Lng is a bridging bond which may independently be a single carbon-carbon bond, an ether bond, a sulphide bond, 2-6 sulfur atoms polysulfide bond, sulfinyl bond, sulfonyl bond, lower alkylene bond, di- (lower alkyl) methylene bond, lower alkylene ether bond, lower alkylene sulfide bond, lower 3-aryloxy group Composition according to Claim 1, characterized in that Ar is a benzene nucleus having 0 to 3 possible substituents and a, b and c are each 1. Composition according to Claim 4, characterized in that R is a substituent containing an average of about 30 aliphatic carbon atoms and is derived from homopolymerized or interpolymerized C 2 -C 10 olefins. Composition according to Claim 12, characterized in that the 1-olefin is ethylene, propylene, butylene and a mixture thereof. 14 *. Composition according to Claim 1, characterized in that the aminophenol has the formula r, n. . 30 0-6255ϋ R-Ij-I- <NH2> 1-2 X <R '> z wherein R is a predominantly saturated hydrocarbon-based substituent having an average of about 30 to about 750 aliphatic carbon ethanes; R 'is lower alkyl, lower alkoxyl, nitro or halogen; and z is 0 or 1, provided that R is in the ortho or para position relative to the phenolic hydroxyl group. Composition according to Claim 14, characterized in that R contains at least 50 aliphatic carbon atoms. Composition according to Claim 14, characterized in that R is a substantially saturated, purely aliphatic group. Composition according to Claim 14, characterized in that R is in the para-position relative to the OH substituent and z is 0. Composition according to Claim 16, characterized in that R is an alkyl or alkenyl substituent. Composition according to Claim 18, characterized in that R contains on average at least about 50 aliphatic carbon atoms. Composition according to Claim 14, characterized in that R is a substituent derived from homopolymerized or interpolymerized C2-10 olefins. Composition according to Claim 20, characterized in that the C 2 -C 10 olefins are C 2 -C 4 olefins or mixtures thereof. Composition according to Claim 21, characterized in that the 1-olefin is ethylene, propylene, butylene or a mixture thereof. Composition according to Claim 1, characterized in that the aminophenol has the formula 31 ° Η 6255ύ <h 2 N) 0-1 JL ^ NH 2 (R 1) i-ί R contains an average of about 30 to about 750 aliphatic carbon atoms; R 'is lower alkyl, lower alkoxyl, nitro or halogen; and z is 0 or 1. Composition according to Claim 23, characterized in that the 1-olefin is ethylene, propylene, butylene or a mixture thereof. Composition according to Claim 24, characterized in that R is derived from polymerized isobutene. A composition according to claim 25, characterized in that R is an alkyl or alkenyl group containing on average at least about 50 aliphatic carbon atoms. Composition according to Claim 26, characterized in that z is 0. 28. A fuel or lubricant composition having more than normal liquid fuel or lubricating oil having a lubricating viscosity and less than an amino-containing composition, characterized in that the amino-containing additive is prepared by (I) nitrating at least one compound of formula (OH) I c ( R) -Ar 'SL wherein R is a predominantly saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a and c are each independently an integer from 1 to 3 times the number of aromatic nuclei present in the Ar group, provided that the sum of the numbers a, b and c does not exceed the number of unsaturated valencies in the Ar 'group; and Ar 'is an aromatic group having 0 to 3 possible substituents such as lower alkyl, lower alkoxyl, nitro or halogen, or a combination of two or more such possible substituents; provided that (a) Ar 'contains at least one hydrogen atom directly attached to a carbon atom which forms a./'·'. . M 32 6255b represents part of the aromatic ring, and (b) when Ar is benzene having only one hydroxyl and only one R substituent, the R substituent is ortho or para to said hydroxyl substituent to form a first reaction mixture containing nitro intermediate, and (II) reducing at least about 50% of the nitro groups in said first reaction mixture to amino groups. Composition according to Claim 28, characterized in that R contains on average at most about 750 aliphatic carbon atoms. Composition according to Claim 28, characterized in that Ar 'contains at least one hydrogen atom which is directly bonded to the carbon atom of the aromatic ring, this carbon atom being at an uneven number of carbon atoms from the aromatic carbon atom containing the hydroxyl group. Composition according to Claim 30, characterized in that R contains on average at most about 300 carbon atoms. The composition of claim 31, wherein R contains at least about 30 carbon atoms and is derived from homopolymerized or interpolymerized C 2 -C 10 olefins. Composition according to Claim 32, characterized in that Ar 'is a benzene nucleus. Composition according to Claim 28, characterized in that the nitrating agent is nitric acid. Composition according to Claim 28, characterized in that the nitro medium is reduced with hydrogen in the presence of a metal hydrogenation catalyst. Composition according to Claim 28, characterized in that the amino-containing additive ori is prepared (I) by nitration with a nitrating agent of at least one compound of the formula OH (R '") ---- fR' wherein R 'is a substantially saturated hydrocarbon-based substituent f *' : has an average of about 30 to about 750 aliphatic carbon atoms / ortho or para to the hydroxyl group, R '' 'is Lower alkyl, lower alkoxyl, nitro or halogen, z is 0 or 1, to form a first reaction mixture containing a nitro intermediate, (II) by reducing at least about 50% of the nitro groups in the first reaction mixture to amino groups. Composition according to Claim 36, characterized in that R 'is in the para position with respect to the hydroxyl group and is derived from homopolymerized isobutylene and z is 0. Composition according to Claim 28 or 36, characterized in that the amino-containing composition is prepared by reducing at least about 50% of the nitro groups to amino groups in a compound or mixture of compounds of the formula (OH) ic (R) j-Ar-O »>> R is a predominantly saturated hydrocarbon-based substituent having at least 10 aliphatic carbon atoms; a, b and c are each independently an integer from 1 to 3 times the number of aromatic nuclei in the group Ar, provided that the sum of the numbers a, b and c does not exceed the number of unsaturated valencies in the group Ar; and Ar is an aromatic group having 0 to 3 possible substituents selected from lower alkyl, lower alkoxyl, halogen, or a combination of two or more of said possible substituents; provided that when Ar is a benzene nucleus having only one hydroxyl and only one R substituent, the R substituent is in the ortho or para position relative to the hydroxyl substituent. Composition according to Claim 38, characterized in that the at least one nitro substituent is reduced with hydrogen in the presence of a metallic hydrogenation catalyst. i · 1 ",» '\ 34 6. S 5 ϋ