JPS627184B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to novel compounds useful as lubricants based on oils having lubricating viscosity and as additives for normally liquid fuels, and more particularly to novel compounds containing at least one hydrocarbon group having at least about 10 aliphatic carbon atoms. The present invention relates to an aminophenol containing US Pat. No. 2,197,835 discloses a method for producing metal salts of aromatic amines produced by nitration and reduction of wax-substituted hydroxyaromatic hydrocarbons. This metal salt can be added to mineral oil to lower the pour point of the mineral oil or to improve the viscosity index of the mineral oil. US Pat. Nos. 2,502,708 and 2,571,092 describe a process for producing amines of cardanol by nitration and subsequent reduction of cardanol. The aminocardanol is said to be useful as an antioxidant for mineral oils, fats and petroleum. Cardanol, also known as anacardol, is 3-pentadecylphenol 3-(8'-pentadecenyl)phenol, 3-(8':11'pentadecadienyl)phenol and 3-(8:11:14'-pentadecylphenol). It is also described as a mixture of decatrienyl)phenols. In addition to the structural formulas described in the above two patent publications, the literature (The Dictionary of Organic Compounds, Vol. 1, Oxford)
University Press (1965), p. 229) shows that the C ₁₅ substituent in cardanol is in the meta position relative to the hydroxyl group. U.S. Pat. No. 2,859,251 discloses ortho-, para-, and meta-aminophenols containing 6 to 18 carbon atoms per molecule in the presence of a complex catalyst obtained by mixing hydrogen fluoride with boron trifluoride and fluorides of iron metals. A method of alkylation with an olefin polymer having atoms is described. It is not clear from this patent whether the alkyl groups in the product mixture are bonded to carbon, nitrogen and/or oxygen atoms. The use of additives to improve the performance properties of lubricating oils and normally liquid fuels based on oils of lubricating viscosity (eg, oils and greases) has been practiced over the past several decades. However, today, with increasingly scarce raw materials, inflationary equipment replacement costs, rising fuel and lubricant prices, and environmental concerns, new and effective lubricants and fuels are becoming available. We cannot stop the development of additives for this purpose. Accordingly, it is an object of this invention to provide new aminophenol compounds capable of imparting useful and desirable properties to oil-based lubricants and normally liquid fuels. A further object of the invention is to provide novel concentrates and lubricants and fuels containing the novel aminophenol compounds of the invention. Other objects of the invention will become apparent from the following description. This invention is based on the formula (In the above formula, R is a substantially saturated hydrocarbon substituent having at least 10 aliphatic carbon atoms;
a, b and c are each independently a number from 1 to 3 times the number of aromatic nuclei present in Ar, and the sum of a, b and c does not exceed the effective valence of Ar, and Ar is a lower An aromatic moiety that may have 0 to 3 substituents selected from the group consisting of an alkyl group, a lower alkoxyl group, a nitro group, a halo group, and a combination of two or more of these, provided that Ar is a hydroxyl group and R In the case of a benzene nucleus each having only one group, the R group consists of aminophenols represented by (positions ortho or para to the hydroxyl group). As used herein, the term "phenol" has its art-recognized general meaning and refers to hydroxyaromatic compounds having at least one hydroxyl group directly attached to a carbon of an aromatic ring. Also within embodiments of this invention are oil-based lubricants, usually liquid fuels, and additive concentrates of lubricating viscosity containing the aminophenols described above. The aromatic moiety Ar in the aminophenol is a benzene nucleus, a pyridine nucleus, a thiophene nucleus, 1, 2,
It does not matter whether it is a mononuclear aromatic nucleus such as 3,4-tetrahydronaphthalene nucleus or the like, or a polynuclear aromatic moiety. This polynuclear aromatic moiety is of the fused type, i.e. naphthalene, anthracene,
As seen in azanaphthalenes, at least two aromatic nuclei may be condensed with other nuclei at two locations. Further, the polynuclear aromatic moiety may be of a crosslinked type, that is, at least two nuclei (mononuclear or polynuclear) are bonded to each other through a crosslinking bond. Such cross-linking bonds include carbon-carbon double bonds, ether bonds, keto bonds, sulfide bonds, polysulfide bonds having 2 to 6 sulfur atoms, sulfinyl bonds, sulfonyl bonds, methylene bonds, alkylene bonds, di(lower alkyl) bonds, methylene bond, lower alkylene ether bond, alkylene keto bond,
It can be selected from the group consisting of lower alkylene sulfur bonds, lower alkylene polysulfide bonds having 2 to 6 sulfur atoms, amino bonds, polyamino bonds, and combinations of these divalent crosslinking bonds. In some cases, one or more crosslinks may exist between the aromatic nuclei in Ar. for example,
In the fluorene nucleus, two benzene nuclei are bonded by a methylene bond and a covalent bond. Such a nucleus is thought to have three nuclei, only two of which are aromatic. Usually, Ar contains only carbon atoms in the aromatic nucleus itself. The number of aromatic nuclei (condensed type, crosslinked type, or both) in Ar is a, b in the above formula ()
and determine the numerical value of c. for example,
When Ar contains a mononuclear aromatic nucleus, each of a, b and c is independently 1 to 3.
If Ar contains two aromatic nuclei, each of a, b and c is from 1 to 6, ie up to three times the number of aromatic nuclei present (2 in naphthalene). For the trinuclear Ar moiety, a, b
and c are each from 1 to 9. For example, when Ar is biphenyl, each of a, b and c is independently 1 to 6. Of course, the values of a, b and c are limited by the fact that they do not exceed the total effective valence number of Ar. The monocyclic aromatic nucleus that is the Ar moiety has the general formula ar(Q) _n (in the above formula, ar is a monocyclic aromatic nucleus having 4 to 10 carbon atoms (for example, benzene), and each Q is independently a lower alkyl group. , a lower alkoxy group, a nitro group or a halogen atom, and m can be represented by 0 to 3). In this specification and claims, the term "lower" used in groups such as lower alkyl and lower alkoxyl refers to groups having 7 or less carbon atoms. Furthermore, halogen atoms include fluorine, chlorine, bromine, and iodine groups. Typically, halogen atoms are fluorine and chlorine atoms. Specific examples of the above monocyclic Ar moiety are listed below.

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. In the above formula, Me is methyl, Et is ethyl,
Pr is normal propyl and Nit is nitro. When Ar is a polynuclear fused ring aromatic moiety, this is expressed as (In the above formula, ar, Q, and m are as described above, m' is 1 to 4, and 〓 is a pair of two rings condensed to produce two carbon atom moieties of each ring of two adjacent rings.) ) can be shown as a condensed bond. Fused ring type aromatic moiety
Specific examples of Ar are listed below. When the aromatic moiety Ar is a crosslinked polynuclear aromatic moiety, it is expressed by the general formula ar-(Lng-ar-) _w -(Q) _nw (in the above formula, w is 1 to about 20, and ar is the above-mentioned with at least three free valences present in all ar, Q and m as above, and each Lng is a carbon-carbon single bond,
Ether bonds (e.g. -0-), keto bonds (e.g.

[Formula]), sulfide bond (e.g. -S-), polysulfide bond containing 2 to 6 sulfur atoms (e.g. -S _2-6 -), sulfinyl bond (e.g. -
S(O)-), sulfonyl bond (e.g. -S(O)
₂ −), lower alkylene bonds (e.g., −CH ₂ −,
−CH ₂ −CH ₂ −,

[Formula], etc.), di(lower alkyl)methylene bonds (e.g. -CR ⁰ ₂ -), lower alkylene ether bonds (e.g. -CH ₂ O
−, −CH ₂ O−CH ₂ −, −CH ₂ −CH ₂ O−, −
CH ₂ CH ₂ OCH ₂ CH ₂ −,

【formula】

[Formula], etc.), lower alkylene Keto bonds (e.g.

【formula】

[Formula]), lower alkylene sulfide bonds (for example, one or more -O- in the above alkylene ether bond is replaced with -S- atoms), lower alkylene polysulfide bonds (for example, − in the above alkylene ether bond
one or more of O- is replaced by an -S _2-6 - group), an amino bond (e.g.

【formula】

【formula】 【formula】

【formula】

[Formula] (alK is lower alkylene, etc.), poly Amino bonds (e.g.

[Formula] where the valence of free N is satisfied by H or R ⁰ group) and combinations of these crosslinking bonds (each R ⁰ above is a lower alkyl group) This can be shown as a cross-linked bond. Specific examples of the crosslinked type polynuclear aromatic moiety Ar are listed below.

【formula】

【formula】

【formula】 【formula】

etc. Typically, all these Ar moieties are unsubstituted except for the R, -OH and _-NH2 groups (and bridging groups). Due to reasons such as price, availability, and performance,
The Ar moiety is typically a benzene nucleus, a lower alkylene bridged benzene nucleus, or a naphthalene nucleus. That is, a typical Ar moiety is a benzene or naphthalene with 3 to 5 available valencies, one or two of which are filled by a hydroxyl group, and the remaining available valencies are filled as much as possible. , which may be located at the ortho or para position relative to the hydroxyl group. Preferably, Ar has one effective valence filled by a hydroxyl group and the remaining two or three.
It is a benzene nucleus having three or four effective valences such that one effective valence can be located in the ortho position and in the para position with respect to the hydroxyl group. The aminophenol of this invention has an aromatic moiety Ar
an aliphatic carbon atom directly bonded to at least about
10 substantially saturated monovalent hydrocarbon groups R
Contains. The R group can have up to about 400 aliphatic carbon atoms. More than one such R group may be present, but usually there will be at most two or three for each aromatic nucleus in the aromatic moiety Ar. The total number of R groups is indicated by the numerical value of "a" in the above formula (). Typically, the hydrocarbon group will have at least about 30, more typically at least about 50, and up to about 750, more typically about
It has up to 400, usually up to 300 aliphatic carbon atoms. Typically this R group is an alkyl or alkenyl group. Generally, the hydrocarbon group R is a homopolymer of mono- and diolefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. Derived from interpolymers (e.g. dipolymers, terpolymers). Typically, these olefins are 1-monoolefins. R groups can also be derived from halogenated (eg, chlorinated or brominated) versions of the above homopolymers or interpolymers. This R group is a high molecular weight alkene monomer (e.g. 1-
tetracontent) and its chlorides and hydrochlorides, aliphatic petroleum fractions, paraffin waxes and their chlorides and hydrochlorides, white oil, alkenes obtained by the Ziegler-Natsuta process (e.g.
It can also be derived from sources such as synthetic alkenes such as poly(ethylene) grease) and other sources known in the art. Any unsaturation present in the R group may be reduced or removed by hydrogenation according to methods known in the art prior to nitration as described below. "Hydrocarbon-based" in this specification means a radical having a carbon atom directly bonded to the remainder of the molecule and having predominantly hydrocarbon character within the meaning of the present invention. Thus, a hydrocarbon group can contain up to one non-hydrocarbon group for every ten carbon atoms. However, this non-hydrocarbon group must not significantly change the main hydrocarbon properties of the hydrocarbon group. Such non-hydrocarbon groups will be apparent to those skilled in the art. For example, hydroxyl groups, halo groups (especially chloro and fluoro groups), alkoxyl groups, alkylmercapto groups,
Such as an alkylsulfoxy group. Usually, the hydrocarbon group R is purely hydrocarbyl and does not contain any non-hydrocarbon groups as described above. The hydrocarbon group R is substantially saturated.
That is, for every 10 carbon-carbon double bonds present, there is at most one carbon-carbon unsaturated bond. Usually, R is the 50 carbon-carbon bonds present.
Each carbon-carbon non-aromatic unsaturated bond contains at most one carbon-carbon non-aromatic unsaturated bond. The hydrocarbon groups of the aminophenols of this invention are also substantially aliphatic in nature. That is, a non-aliphatic group having 6 or less carbon atoms (cycloalkyl group,
cycloalkenyl group or aromatic group) is at most one. They usually contain no more than one such non-aliphatic group per 50 carbon atoms, and often no such non-aliphatic groups at all. That is, a typical R
The radicals are purely aliphatic. Typically these pure aliphatic R groups are alkyl or alkenyl groups. Specific examples of the substantially saturated hydrocarbon group R are listed below. Tetra (propylene) group, deca (propylene) group, tri (isobutene) group, trideca (isobutene) group, tetracontanyl group, hempentacontanyl group, poly(ethylene/
mixtures of oxidatively modified or mechanically modified poly(ethylene/propylene) groups having from about 35 to about 70 carbon atoms, poly(propylene/1-hexene) having from about 80 to about 150 carbon atoms; mixtures of poly(isobutene) radicals having from 20 to 32 carbon atoms; mixtures of poly(isobutene) radicals having on average from 50 to 75 carbon atoms. Typically, the R group is ethylene, propylene,
C ₂ ~ like butenes and mixtures thereof
Derived from homopolymers or interpolymers of C ₁₀ 1-olefins. A preferred source of R groups is
butene content 35 to 75% by weight and isobutene content 15 to 60, typically 30 to 60% by weight
These are poly(isobutenes) obtained by polymerizing the C4 fraction of ₂₀₀₀ in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes are primarily (i.e., 80% of the total repeating units)
above) formula Contains an isobutene repeating unit represented by A number of methods familiar to those skilled in the art can be used to attach the hydrocarbon group R to the aromatic moiety Ar of the aminophenols of this invention. One particularly suitable method is the Friedel-Crafts reaction, in which olefins (for example polymers with olefinic bonds) or their halides or hydrohalides are reacted with phenols. This reaction is carried out in the presence of a Lewis acid catalyst (for example, boron trifluoride and its complexes with ethers, phenols, hydrogen fluoride, etc., aluminum chloride, aluminum bromide, zinc dichloride, etc.). Procedures and conditions for carrying out this reaction are well known to those skilled in the art. For example, "Encyclopedia of Chemical Technology" by Kirk Osmer, published by Interscience Publishers, 2nd edition, 1st edition.
See "Alkylation of Phenols" in Vol. 894-895 (1963).
Equally suitable and convenient methods for attaching the hydrocarbon group R to the aromatic moiety Ar will be apparent to those skilled in the art. As can be easily seen from the above formula (), the aminophenol of the present invention contains at least one of each of the following substituents. The substituents include a hydroxyl group, the above-mentioned R group, and a primary amine group.
It is _NH2 . Each of these groups is bonded to a carbon atom that is part of the aromatic nucleus in the Ar moiety.
However, when two or more aromatic nuclei are present in the Ar moiety, it is not necessary that each of the substituents be bonded to the same aromatic ring. In certain preferred embodiments, the aminophenols of the invention contain one of each of the above substituents and a mononuclear aromatic ring, preferably benzene. This preferred aminophenol has the formula (In the above formula, R′ represents about 30 to about 30 aliphatic carbon atoms located at the ortho or para position of the hydroxyl group.
R is a lower alkyl group, a lower alkoxyl group, a nitro group, or a halogen atom, and z is 0 or 1). Usually z is 0, and
R' is a substantially saturated pure aliphatic group. Often R' is an alkyl or alkenyl group para to the -OH group. Other preferred aminophenols of this invention have the formula (In the above formula, R is a substantially saturated hydrocarbyl group having an average of about 30 to about 750 aliphatic carbon atoms, R' is a lower alkyl group, a lower alkoxyl group, a nitro group, or a halogen atom, and z
is 0 or 1, where R is at the ortho or para position of the hydroxyl group). Still other preferred aminophenols have the formula (In the above formula, R″ is a group derived from a C ₂ -C ₁₀ 1-olefin homopolymer or interpolymer having an average of about 30 to about 300 aliphatic carbon atoms, and R and z are as defined above. Typically R'' is derived from ethylene, propylene, butylene or a mixture thereof. Typically R'' is a polymer of isobutene. Often R'' has at least about 50 aliphatic carbon atoms and z is zero. Also, other preferred aminophenols have the formula (In the above formula, R is a group derived from a C ₂ -C ₁₀ 1-olefin homopolymer or interpolymer and has an average of about 30 to about 750 aliphatic carbon atoms; R' is a lower alkyl group, a lower alkoxyl group, a nitro group or a halo group, and z
is 0 or 1, provided that when there is only one amino group at the ortho position of the hydroxyl group, R' may be located at the ortho position of the hydroxyl group. In this case R often has on average at least 50 aliphatic carbon atoms and is derived from homopolymers or interpolymers of ethylene, propylene, butenes or mixtures thereof. R groups derived from polymers of isobutene are typical. The aminophenols of this invention can be made by a number of synthetic techniques. The techniques vary in the type of reactions used and their order. For example, an aromatic hydrocarbon such as benzene is alkylated with an alkylating agent such as a polymerized olefin to produce an alkylated aromatic intermediate. This intermediate is nitrated to produce, for example, a polynitro intermediate. This polynitro intermediate is then reduced to a diamine, which is diazotized and reacted with water to convert one of the amino groups to a hydroxyl group, thus yielding the desired aminophenol. Alternatively, converting one of the nitro groups in the polynitro intermediate to a hydroxyl group by melting with caustic to obtain a hydroxy-nitroalkyl aromatic intermediate, which is then reduced to obtain the desired aminophenol. You can also do it. Another useful means for producing the aminophenols of this invention involves alkylating phenols with olefinic alkylating agents to produce alkylated phenols. The desired aminophenol is obtained by nitrating the alkylated phenol to produce a nitrophenol intermediate and then reducing at least some of its nitro groups. Methods for alkylating phenols are well known to those skilled in the art, as set forth in the Encyclopedia of Chemical Technology, supra. Processes for nitration of phenols are also well known. For example, the aforementioned Encyclopedia of Chemical Technology, 2nd edition, Volume 13, 888
"Nitrophenols" section below, as well as "Aromatic Substances; Nitrations and Halogenations" by PBD de la Mare and JH Rid, published by Academic Press, 1959, Cambridge University. City Press, 1961, “Nitration and Aromatic Reactivity” by J.G. Hoggett, and Interscience Publishers, 1969, “The Chemistry of the Nitro and Aromatic Reactivity”, edited by Henry Feuell.
See "Groups." Aromatic hydroxy compounds can be nitrated with nitric acid, mixtures of nitric acid with sulfuric acid or boron trifluoride, nitrogen tetroxide, nitronium tetrafluoroborate or acyl nitrate. Generally, the concentration e.g. about 30-90%, often about 60-90%
of nitric acid is a convenient nitrating agent. Substantially inert liquid diluents and solvents, such as acetic acid and butyric acid, aid in the progress of the reaction by facilitating contact between the reactants. Conditions and concentrations for nitrating hydroxyaromatic compounds are well known in the art. For example, the reaction can be carried out at a temperature of about -15°C to about 150°C. Usually, nitration is conveniently carried out at about 25 to 75°C. Generally, about 0.5 to 4 moles of nitrating agent are used for each mole of aromatic nuclei present in the hydroxyaromatic compound to be nitrated, depending on the nitrating agent used. If more than one aromatic nucleus is present in the Ar site, the amount of nitrating agent can be increased proportionally depending on the number of aromatic nuclei. For example, since one mole of naphthalene-based aromatic intermediate has two "monocyclic" aromatic nuclei for purposes of this invention, about 1 to 4 moles of nitrating agent are generally used. When nitric acid is used as the nitrating agent, it is used in an amount of about 1.0 to about 3.0 moles per mole of aromatic nuclei. If the reaction is to be carried out quickly, the nitrating agent may be used in an excess of about 5 molar amounts (corresponding to "monocyclic" aromas). Nitration of hydroxyaromatic intermediates generally involves
It takes 0.25 to 24 hours. However, it is advantageous to react the nitration mixture for a long time, for example 96 hours. The reduction of aromatic nitro compounds to the corresponding amines is well known. For example, see the section ``Amination by Reduction'' in the aforementioned ``Encyclopedia of Chemical Technology,'' 2nd edition, Volume 2, pages 76-99. Generally, this reaction can be carried out with, for example, hydrogen, carbon monoxide or hydrazine (or mixtures thereof) in the presence of a metal based catalyst such as palladium, platinum and its oxides, copper chromite. Cocatalysts such as alkali metal or alkaline earth metal hydroxides or amino acids (including aminophenols) can also be used in this catalytic reduction. Reduction can also be carried out using a reducing metal in the presence of an acid such as hydrochloric acid. Typical reducing metals are zinc, iron and tin, and salts of these metals can also be used. The nitro group can also be reduced by the ginine reaction described in "Organic Reactions", Chillon, Willey & Sons, 1973, Vol. 20, pp. 455 et seq. Generally, the ginine reaction involves the reduction of a nitro group by divalent negative compounds such as alkali metal sulfides, polysulfides, and hydrosulfides. Nitro groups can also be reduced by electrolysis. See, for example, "Amination by Reduction" above. Typically, the aminophenols of this invention are obtained by reducing nitrophenol with hydrogen in the presence of the metal catalysts described above. This reduction is generally approximately
Temperatures of 15-250℃, typically about 50-150℃, about 0
It is carried out under hydrogen pressure of ~2000 psig, typically about 50-250 psig. The reduction reaction time varies between about 0.5 and 50 hours. Substantially inert liquid diluents and solvents such as ethanol, cyclohexane, and the like can be used to facilitate this reaction. Aminophenol products may be obtained by distillation, filtration, extraction, or other well known means. The reduction is carried out until at least about 50%, and usually about 80%, of the nitro groups present in the nitro intermediate are converted to amino groups. A typical method for obtaining the aminophenols of this invention just described is summarized below. ()formula (In the above formula, R is a substantially saturated hydrocarbon group 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 Ar, and a, b
and the sum of c does not exceed the effective valence of Ar′,
Ar′ is an aromatic moiety having 0 to 3 substituents selected from the group consisting of a lower alkyl group, a lower alkoxyl group, a nitro group, a halo group, and a combination of two or more of these groups, provided that (a) Ar ' has at least one hydrogen atom directly bonded to a carbon atom that is part of the aromatic nucleus, and (b) when Ar' is benzene having only one hydroxyl group and one R group, the R group is a hydroxyl group. nitrating with at least one nitrating agent a first reaction mixture containing a nitro intermediate; The method reduces at least about 50% of the nitro groups in the first reaction mixture to amino groups. Typically, what we have described above is equivalent to the formula (In the above formula, R is a substantially saturated hydrocarbon group having at least 10 aliphatic carbon atoms, a,
b and c are each independently a number from 1 to 3 times the number of aromatic nuclei present in Ar, and a, b
and the sum of c does not exceed the effective valence of Ar,
Ar is an aromatic moiety that may have 0 to 3 substituents selected from the group consisting of a lower alkyl group, a lower alkoxyl group, a halo group, and a combination of two or more of these, provided that Ar is only one In the case of a benzene nucleus having a hydroxyl group and one R group, the R group is located in the ortho or para position of the hydroxyl group. It means. Other typical methods for obtaining certain aminophenols of this invention are summarized below. () expression (In the above formula, R is a substantially saturated hydrocarbyl group having about 30 to about 750 aliphatic carbon atoms, and R' is selected from the group consisting of lower alkyl, lower alkoxy, nitro, and halo groups. nitrating at least one of the compounds represented by a selected substituent, z being 0 or 1) with at least one nitrating agent to produce a first reaction mixture containing a nitro intermediate, and () The method reduces at least about 50% of the nitro groups in the first reaction mixture to amino groups. Usually the nitrating agent is nitric acid and the reduction is carried out using hydrogen in the presence of a metallic hydrogenation catalyst. The R group is in the ortho or para position of the phenolic hydroxyl group. Examples of this invention will be described below. In this specification, as well as in the claims, all "parts" and "%" in the following examples are by weight unless indicated otherwise. Example 1A A mixture of 361.2 parts of tetrapropenyl-substituted phenol and 270.9 parts of glacial acetic acid was heated at 7-17°C.
with 90.3 parts of nitric acid (70-71% _HNO3 ) and glacial acetic acid
A mixture consisting of 90.3 parts was added. This addition is done while the reaction mixture is externally cooled and kept at 7-17°C.
It took me 1.5 hours. The cooling bath was removed and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was then stripped at 134° C./35 Torr and filtered to yield the desired nitrated intermediate as a filtrate with a nitrogen content of 4.65%. Example 1B A mixture consisting of 150 parts of the product of Example 1A and 50 parts of ethanol was charged to an autoclave. The mixture was degassed by bubbling nitrogen and 0.75 part palladium on charcoal was added. The autoclave was degassed and pressurized with nitrogen several times and then placed under 100 psig hydrogen pressure. The reaction mixture was heated to 95 to 100°C.
It was held for 2.5 hours. Meanwhile, hydrogen pressure is from 100 psig.
It changed to 20 psig. When the hydrogen pressure dropped below 30 psig, it was adjusted back to 100 psig. The reaction was continued for 20.5 hours at which point the autoclave was opened and an additional 0.5 parts of palladium on charcoal was added. After three cycles of nitrogen bubbling, the autoclave was repressurized with hydrogen to 100 psig and the reaction continued for an additional 16.5 hours. A total of 1.63 moles of hydrogen were charged to the autoclave. The reaction mixture was filtered and stripped to 130°C/16 Torr. Another filtration yielded a product with a nitrogen content of 4.78%. Example 2A 3685 parts of polyisobutene-substituted phenol (the polyisobutene substituent contained 22 to 25 carbon atoms) and textile benzene
790 parts of nitric acid (70%) were added to the mixture consisting of 1400 parts. The reaction temperature was kept below 50°C. After stirring for about 0.7 hours, the reaction mixture was poured into 5000 parts of ice and left for 16 hours. The separated organic layer was washed twice with water, and then 1000 parts of benzene was added. The solution was stripped to 170°C and the residue was filtered to determine the nitrogen content.
The desired intermediate with a viscosity of 2.41% and a viscosity at 99°C of 150.8 SUS was obtained. Example 2B A mixture consisting of 130 parts of the product of Example 2A, 130 parts of ethanol and 0.2 parts of platinum oxide (PtO ₂ ) was charged to a hydrogenation bomb. The bomb was bubbled with hydrogen several times and then pressurized to 54 psig with hydrogen. The cylinder was rocked for 24 hours and charged with hydrogen again to 70 psig. Rocking was continued for an additional 98 hours. The resulting reaction mixture was stripped to 145°C/760 Torr to yield the desired product. Example 2C A mixture of 420 parts of the product of Example 2A, 326 parts of ethanol, and 12 parts of commercially available nickel on diatomaceous earth was charged to an appropriately sized hydrogenation bomb. The bomb was pressurized with hydrogen to 1480 psig and shaken for 5.25 hours. The resulting reaction mixture was stripped to 65° C./30 Torr to yield the desired product as a residue with a nitrogen content of 2.62%. Example 2D 105 parts of the product of Example 2A, 303 parts of cyclohexane
A mixture of 50% and a commercially available Raney Nickel catalyst was charged into an appropriately sized hydrogenation bomb. The bomb was pressurized with hydrogen to 1000 psig and shaken at approximately 50°C for 16 hours. The cylinder was again pressurized to 1100 psig and vibrated for an additional 24 hours. The bomb was then opened and the reaction mixture was filtered and charged back into the bomb along with 4 parts of fresh Raney Nickel catalyst. The cylinder was pressurized to 1100 psig and vibrated for 24 hours. The resulting reaction mixture was stripped to 95°C/28 Torr to obtain a product with a hydrogen group content of 5.24% and a nitrogen content of 2.25%. Example 3A Alkylated phenol was produced by reacting phenol with polyisobutene having a number average molecular weight of about 1000 (vapor phase osmotic pressure method) in the presence of a boron trifluoride-phenol complex catalyst. This product was first heated at 230℃/
The purified alkylated phenol was obtained by stripping to 760 Torr (steam temperature) and then to 205°C (steam temperature)/50 Torr. A mixture of 18.4 parts of concentrated nitric acid (69-70%) and 35 parts of water was slowly added to a mixture of 265 parts of the purified alkylated phenol, 176 parts of blended oil, and 42 parts of petroleum naphtha having a boiling point of about 20°C. The reaction mixture was stirred at approximately 30-45°C for 3 hours, then 120°C/
Stripping to 20 torr and filtration provided an oil solution of the desired nitrophenol intermediate. Example 3B A mixture consisting of 1500 parts of the product solution of Example 3A, 642 parts of isopropanol, and 7.5 parts of diatomaceous earth supported nickel catalyst was charged into an autoclave under a nitrogen atmosphere. Nitrogen bubbling and degassing 3
After several cycles, replace the autoclave with hydrogen.
Pressurized to 100 psig and started vibrating. The reaction mixture was held at 96°C for a total of 14.5 hours. In all that time
1.66 moles of hydrogen were supplied. After nitrogen bubbling three times, the reaction mixture was filtered and the filtrate was
Stripped to ℃/18 Torr. An oil solution of the desired product containing 0.54% nitrogen was obtained by filtration. Example 4A A mixture of 400 parts of a polyisobutene-substituted phenol (the polyisobutene group contained about 100 carbon atoms), 125 parts of textile benzine and 266 parts of diluted mineral oil was dissolved in 50 parts of water at 28°C. 22.83 parts of nitric acid (70%) was added gradually over 0.33 hours. The mixture was stirred at 28-34°C for 2 hours and 158
Stripped to ℃/30 torr. An oil solution of the desired intermediate with a nitrogen content of 0.88% (40
%) was obtained. Example 4B A mixture consisting of 93 parts of the product oil solution of Example 4A and 93 parts of a mixture of toluene and isopropanol (50/50 parts) was charged to an appropriately sized hydrogenation vessel. After degassing the mixture and bubbling with nitrogen, commercially available platinum oxide (86.4% PtO ₂ ) was added. The reaction vessel was pressurized to 57 psig and held at 50-60°C for 21 hours. A total of 0.6 moles of hydrogen was fed to the reaction vessel. The reaction mixture was then filtered and the filtrate was stripped to yield an oil solution of the desired product containing 0.44% nitrogen. Example 5A Polyisobutene substituted phenol of Example 4A
60 parts of a mixture of 2160 parts and 1440 parts of diluted mineral oil
It was heated to ℃. Then, 25 parts of paraformaldehyde were added to the above mixture, followed by 15 parts of hydrochloric acid.
This mixture was heated to 115°C for 1 hour. 16 at room temperature
After standing for an hour, the reaction mixture was heated to 160°C for 1 hour. During this time, 20 parts of distillate were removed. The reaction mixture was stripped to 160°C/15 Torr to obtain the desired methylene-bridged polyisobutene-substituted phenol solution in oil. Example 5B To 2406 parts of the oil solution obtained in Example 5A and 600 parts of textile benzine, 90 parts of nitric acid (70%) was added over 1.5 hours. The reaction mixture was stirred for 1.5 hours, left at room temperature for 63 hours, then heated to 90° C. for 8 hours.
Stripping to 160°C/18 Torr yielded an oil solution of the desired nitrated intermediate containing 0.79% nitrogen. Example 5C A mixture consisting of 800 parts of the oil solution of Example 5B and 720 parts of a toluene/isopropanol mixture (60/40 parts) was charged to an autoclave. After nitrogen blowing, diatomaceous earth supported nickel catalyst 4
Added a section. After three cycles of nitrogen bubbling, the autoclave was pressurized with hydrogen to 60 psig at 25°C.
The reaction temperature was gradually increased to 96℃ and the pressure was increased.
Keep at 100psig for 5.5 hours. The autoclave was then opened and an additional 4 parts of diatomaceous earth supported catalyst were added. The autoclave was repressurized with hydrogen to 100 psig and maintained at 96° C. and 100 psig for 6 hours. Cool the autoclave, open it and add more platinum oxide catalyst.
Added 0.8 parts. Re-autoclave with hydrogen
Pressure was increased to 90 psig and maintained at this pressure for an additional 8 hours. The reaction mixture was filtered and the filtrate was stripped to 150°C/18 Torr to obtain an oil solution of the desired product with a nitrogen content of 0.41%. Example 6A 1962 parts of polyisobutene-substituted phenol obtained in Example 3A, 49.5 parts of paraformaldehyde, 15 parts of hydrochloric acid
and 1372 parts of diluted mineral oil at 115°C.
It was heated for 7 hours. The reaction temperature was then increased to 160-165°C and held at that temperature for an additional 7 hours. 400 parts of benzine for textiles was added to this mixture and cooled to 30°C. Then 136.95 parts of nitric acid (70%) in 140 parts of water were slowly added. The reaction mixture was stirred at 30-35°C for 1.5 hours and then stripped to 170°C/28 Torr to give an oil solution of the desired intermediate, which was clarified by filtration. Example 6B 96 parts of the oil solution obtained in Example 6A and toluene/
A mixture consisting of 96 parts of an isopropanol mixture (50/50) was charged to an appropriately sized hydrogenation vessel.
After nitrogen blowing, 0.32 parts of platinum oxide catalyst was added. The reaction vessel was again flushed with nitrogen and then pressurized to 157 psig with hydrogen at 25°C. Increase the hydrogen pressure to 57 or
Hold at 50 psig for 6.0 hours, during which time the reaction mixture
Heated to 50-60°C. The reaction mixture thus obtained was filtered and stripped to determine the nitrogen content.
A 0.353% solution of the desired product in oil was obtained. Example 7A 27 consisting of 654 parts of polyisobutene-substituted phenol prepared in Example 3A and 654 parts of isobutyric acid
90 parts of 16 molar nitric acid were added to the mixture at -31°C over 0.5 hour. The reaction mixture was held at 50°C for 3 hours and then at room temperature for 63 hours. Stripping to 160° C./26 Torr and filtration through filter aid yielded the desired nitro intermediate with a nitrogen content of 1.8%. Example 7B The nitro product obtained in Example 7A was hydrogenated using a nickel on diatomaceous earth catalyst following substantially the same method as in Example 3B. Example 8A 4578 parts of polyisobutene-substituted phenol obtained in Example 3A, 3052 parts of diluted mineral oil and textile benzene
The mixture consisting of 725 parts was heated to 60°C and homogenized. 16 mol nitric acid in 600 parts of water after cooling to 30°C
319.5 parts were added to the mixture. Cooling was necessary to keep the mixture below 40°C. After stirring the reaction mixture for an additional 2 hours, 3710 parts thereof were transferred to another reaction vessel. 3710 parts of this were further treated with 127.82 parts of 16 molar nitric acid in 130 parts of water at 25-30°C. The reaction mixture was stirred for 1.5 hours and then stripped to 220°C/30 Torr. An oil solution of the desired intermediate was obtained by filtration. Example 8B The oil solution obtained in Example 8A was hydrogenated using platinum oxide in substantially the same manner as in Example 2B to obtain diaminophenol. Example 9 Dinitro C ₂₅ Alkylated Phenol (Example 8A
), 543 parts of isopropanol, and 200 parts of toluene were heated at 19°C over 0.75 hours with a total of 42 parts of ammonia gas.
Processed with. The reaction mixture was then sparged with H ₂ S gas.
Processed in 147 copies. Ammonia and hydrogen sulfide treatments were carried out by introducing the respective gases into the stirred mixture. Repeat the ammonia treatment with 82 parts of ammonia gas, and finally hydrogen sulfide
Processed in 102 copies. The reaction mixture was stripped to 40°C/60 Torr to obtain a residue, which was diluted with oil.
161 parts and stripped again to 70°C/18 Torr. An additional 161 parts of diluent oil and 35 parts of filter aid were added. The mixture was filtered to obtain a viscous filtrate that was a 40% oil solution of the desired diaminophenol. The nitrations of Examples 10 to 16 shown below are shown in Table A
This was carried out in substantially the same manner as in Example 1A using the hydroxy aromatic compound and nitric acid shown in Example 1A. The reduction of the nitro intermediates in these examples was carried out using the methods described in the examples shown in Table A.

【table】

Table: Example 17A A mixture of 1056 parts of tetrapropyl-substituted phenol and 792 parts of acetic acid was cooled to -9°C, and a mixture of 282 parts of concentrated nitric acid and 264 parts of acetic acid was added. The reaction mixture was stirred at 8-27°C for 5 hours. At this time, external cooling was necessary to maintain the reaction temperature within the above range. The reaction mixture was stripped to 132°C/36 Torr and the residue was filtered to yield the desired nitro intermediate. Example 17B 423 parts of commercially available sodium sulfide were quickly added to a mixture consisting of 680 parts of the intermediate obtained in Example 17A, 340 parts of denatured ethanol, and 100 parts of water. A cooling bath was used to keep the reaction temperature below about 65°C. After stirring for about 1 hour, the reaction mixture was refluxed for 4 hours. The reaction mixture was then bubbled with carbon dioxide for 3 hours at 45-30°C. 500 parts of petroleum naphtha was added and stirred for 16 hours. After adding 500 parts of toluene, the reaction mixture was extracted with 500 parts of water. This extraction was repeated four times, and the water extracts were combined and back-extracted with a mixture of petroleum naphtha and toluene. Combine organic extracts,
Stripping to obtain a residue, which is then blended with oil.
Added 409 copies. This mixture was stripped to 105° C./15 Torr to obtain an oil solution of the desired aminophenol. Example 18A An alkylated phenol was produced by reacting phenol with polybutene having a number average molecular weight of about 1000 (vapor phase osmotic pressure method) in the presence of a boron trifluoride-phenol complex catalyst. After neutralizing the catalyst and filtering it out,
The filtrate was stripped first to 230°C/760 Torr (steam temperature) and then to 205°C/50 Torr (steam temperature) to yield purified alkylated phenols as a residue. 260 parts of the resulting refined alkylated phenol, 176 parts of blended mineral oil and petroleum naphtha with a boiling point of approximately 200°C
Concentrated nitric acid (69-70%) to a mixture of 42 parts 18.4
and 35 parts of water were slowly added.
The reaction mixture was stirred at 30-45°C for 3 hours and then heated to 120°C.
Stripping to °C/20 Torr (steam temperature),
Filtration yielded an oil solution of the desired nitrophenol intermediate. Example 18B 1900 parts of a mineral oil solution (containing 43% mineral oil) of the nitrophenol intermediate obtained in Example 18A was heated to 145° C. under a nitrogen atmosphere. 70 parts of hydrated hydrazine were then added slowly to this solution over a period of 5 hours while maintaining the temperature at about 145°C. The mixture was heated to 160° C. for 1 hour, during which time 56 parts of aqueous distillate were collected. An additional 7 parts of hydrated hydrazine were added and the mixture was held at 140°C for an additional hour. This is 130
Filtration at 0C yielded an oil solution of the desired aminophenol containing 0.3% nitrogen. Example 19 Example except that the polybutene used was a polybutene with a molecular weight of about 500 obtained from n-butene.
The desired aminophenol was obtained by performing the same operation as 18A and 18B. Example 20 Tetrapropenylaminophenol was obtained in the same manner as in Examples 18A and 18B, except that the same molar amount of propylene tetramer was used instead of polybutene. Experimental Example 1 An additive concentrate was prepared by blending the components listed in the table below in the proportions shown in the table.

[Table] The above compositions and were blended with gasoline {gasoline 50:composition 1 (weight ratio)} and this fuel mixture was tested in a Chrysler-West Bend engine to evaluate the status of the piston varnish.
A score of 10.0 indicates cleanliness. The results are shown below. Fuel Mixture Piston Varnish Rating: Contains Composition 8.94 (average of 4 times) Contains Composition 9.2 Contains Composition 6.81 As previously stated, the aminophenols of this invention are useful as additives in preparing lubricant compositions. The lubricant composition mainly acts as a detergent/dispersant. The aminophenols of this invention are particularly useful where the oil encounters cyclic stresses such as those found in high temperature environments and on-off engine operation. The lubricating oil compositions of this invention are based on natural or synthetic lubricating oils or mixtures thereof.
These lubricants include crankcase lubricants for spark ignition and compression ignition internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines. Additionally, the aminophenols of this invention are useful in automatic transmission fluids, transmission lubricants, gear lubricants, metalworking lubricants, pressure fluids, and other lubricating oil and grease compositions. Natural oils include animal and vegetable oils (e.g. castor oil and lard oil), as well as liquid petroleum or paraffinic, naphthenic or mixed paraffinic-naphthenic, solvent-treated or acid-treated mineral lubricating oils. . Oils of lubricating viscosity derived from coal or shale are also useful base oils. Synthetic lubricating oils include carbon and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.), poly(1-hexene), ), poly(1-octene), poly(1-decene), etc. or mixtures thereof, alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes) etc.), polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls), alkylated diphenyl ethers, alkylated diphenyl sulfides, and derivatives thereof,
There are analogues and congeners. Homopolymers and interpolymers of alkylene oxide, as well as derivatives thereof whose terminal hydroxyl groups have been modified by esterification, etherification, etc., also constitute another group of known synthetic lubricating oils.
Examples of this include oils obtained by polymerizing ethylene oxide and propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methylpolyisopropylene glycol ether with an average molecular weight of 1000,
diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol with a molecular weight of 1000 to 1500, etc.) or their mono- and polycarboxylic acid esters, such as acetic acid esters, mixed C ₃ to _{C 8} fatty acid esters or C of tetraethylene glycol ₁₃ oxo acid diester. Other suitable groups of synthetic lubricating oils include dicarboxylic acids (e.g. phthalic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid) dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Consists of esters. Specific examples of these esters are as follows.
Namely, dibutyl adipate, di(2-ethylhexyl) sebacate, dinormalhexyl fumanate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, linoleic acid dimer. 2-ethylhexyl diester, a complex ester of 1 mole of sebacic acid, 2 moles of tetraethylene glycol, and 2 moles of 2-ethylcaproic acid, etc. Esters useful as synthetic oils also include:
There are those made from _C5 - _C12 monocarboxylic acids and polyols, and polyol ethers such as trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Silicone-based oils such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils also constitute another useful group of synthetic lubricants (e.g., tetraethyl silicate, tetraethyl silicate, Isopropyl, tetra(2-ethylhexyl) silicate, tetra(4-methyl-hexyl) silicate, tetra(para-tert-butylphenyl) silicate, hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl) ) siloxanes, poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymerized tetrahydrofurans, and the like. Unrefined, refined and rerefined oils of the types described above may be used in the lubricant compositions of this invention. Unrefined oils are those obtained directly from natural or synthetic sources without additional refining treatment. For example, sierre oil obtained directly by retorting, petroleum oil obtained directly by distillation, or ester oil obtained directly by esterification and used without further treatment are unrefined oils. .
Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps to improve one or more properties. The above purification methods are well known to those skilled in the art. For example, solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by applying the processes used to obtain refined oils to already used refined oils. Such rerefined oils are also known as reclaimed oils and are often further processed by methods to remove spent additives and oil breakdown products. Generally, to obtain a satisfactory lubricant composition, at least one aminophenol of this invention is dissolved or stably dispersed in a proportion of about 0.05 to 30, usually about 0.1 to 15 parts by weight per 100 parts of oil. The lubricant compositions may contain, in addition to the products of this invention, other additives commonly used in lubricants. Such additives include, for example, ash-forming and ashless auxiliary detergent and dispersants, antioxidants, pour point depressants, antifoam agents, extreme pressure agents, and color stabilizers. The aminophenols of this invention can also be used in fuels, where they act as detergent-dispersants, antioxidants and preservatives. The fuel compositions of this invention are typically liquid fuels (typically ASTM Specification D-439
−73 motor gasoline and ASTM
Contains large amounts of hydrocarbonaceous petroleum fractions such as diesel fuel or fuel oil as specified in Specification D-396. Alcohols, ethers, organic nitro compounds, etc. (e.g. methanol, ethanol, diethyl ether, methyl ethyl ether,
Normally liquid fuel compositions consisting of non-hydrocarbons such as
Fuel oils derived from vegetable and mineral sources such as charcoal and coal are within the scope of this invention as well. Fuel oils consisting of mixtures of any of the above may also be used. Examples of such mixtures include gasoline and ethanol, diesel fuel and ether, gasoline and nitromethane, etc. Particularly preferred is gasoline (ie, a mixture of hydrocarbons with a 10% distillation point of 60° C. according to ASTM and a 90% distillation point of about 205° C.). Generally, the fuel composition comprises at least one of the aminophenols of this invention in an amount sufficient to impart antioxidant and/or dispersing, detergent properties to the fuel.
Contains seeds. Usually, this amount will be from about 1 to about 10,000 parts by weight, preferably from 4 to 1,000 parts per million parts of fuel. Preferred gasoline-based fuel compositions generally exhibit excellent engine oil sludge dispersion and cleaning properties, as well as oxidation resistance. The fuel compositions of this invention may contain, in addition to the products of this invention, other additives known in the art. Additives include anti-knock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes (e.g. ethylene dichloride, ethylene dibromide), anti-settling agents/modifiers such as triaryl phosphates, and dyes. , cetane improvers, antioxidants such as 2,6-di-tert-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and their anhydrides, bacterial growth inhibitors, gum inhibitors, These include metal deactivators, demulsifiers, upper cylinder lubricants, anti-icing agents, etc. In preferred fuel compositions of this invention, the aminophenols of this invention are used in conjunction with other ashless dispersants in gasoline. Such ashless dispersants are preferably esters of mono- or polyols and high molecular weight mono- or polycarboxylic acylating agents having an anchor moiety of at least 30 carbon atoms. Such esters are well known in the art. for example,
French Patent No. 139664, British Patent Nos. 981850 and 1055337, as well as US Patent No. 3255108,
Same No. 3311558, Same No. 3331776, Same No. 3346354
No. 3522179, No. 3579450, No. 3579450, No. 3522179, No. 3579450, No.
3542680, 3381022, 3639242, 3697428, 3708522, and British Patent No.
See No. 1306529. Generally, from about 0.1 to about 10.0 parts, preferably from about 1 to about 10 parts, of the aminophenols of this invention are used for each part of the ashless dispersant. In another embodiment of this invention, the aminophenols of this invention are used in combination with Mannitz condensation products made from substituted phenols, aldehydes, polyamines, and aminopyridines. Such condensation products are described in U.S. Pat.
No. 3649659, No. 3558743, No. 3539633, No. 3704308, and No. 3725277. The aminophenols of this invention may be added directly to the fuels and lubricants described above to form fuel or lubricant compositions, or they may be added directly to the fuels and lubricants described above, or they may be added to substantially liquid fuels such as mineral oil, xylene, or any of the normally liquid fuels described above. The concentrate may be diluted with at least one inert, normally liquid organic solvent/diluent to form a concentrate and then added to the fuel or lubricant in sufficient quantity to form the fuel and lubricant composition. good. The above concentrate is
Generally, it will contain from about 30 to about 90% by weight of the aminophenols of this invention. The concentrate may also contain the usual additives mentioned above, preferably ashless dispersants, in the proportions mentioned above. The remainder of this concentrate is solvent/diluent.

Claims (1)

[Claims] 1 formula (In the above formula, R is a substituent bonded to the aromatic nucleus in Ar and is a substantially saturated hydrocarbon substituent having at least 30 aliphatic carbon atoms, and a, b and c are each independently 1 or an integer up to three times the number of aromatic nuclei present in Ar, and the sum of a, b and c does not exceed the effective valence number of Ar.
and Ar is an aromatic moiety having 0 to 3 substituents selected from the group consisting of a lower alkyl group, a lower alkoxy group, a nitro group, a halo group, and a combination of two or more of these, provided that Ar is a hydroxyl group and In the case of benzene nuclei each having only one R group, the R group is located in the arso or para position of the hydroxyl group). 2. The aminophenol of claim 1, wherein R has on average up to about 750 aliphatic carbon atoms. 3. The aminophenol according to claim 2, wherein R is a pure hydrocarbyl group. 4. The aminophenol according to claim 3, wherein R is an alkyl group or an alkenyl group. 5. The aminophenol according to claim 1, wherein R is a group derived from a homopolymer or interpolymer of _C2 to _C10 olefins. 6. The aminophenol of claim 5, wherein the _C2 - _C10 olefin is selected from the group consisting of _C2 - _C101 -olefins and mixtures thereof. 7. The aminophenol of claim 6, wherein the 1-olefin is selected from the group consisting of ethylene, propylene, butylene and mixtures thereof. 8. The aminophenol according to claim 1, wherein Ar has two or more bridged and/or condensed polynuclear aromatic nuclei. 9. The aminophenol according to claim 8, wherein Ar is a naphthalene nucleus. 10 Ar has the formula ar−(Lng−ar−) _w −(Q) _nw (where ar is a monocyclic or fused ring nucleus having 4 to 10 carbon atoms and at least 3 effective atoms in all ar) value exists, w is an integer from 1 to 20,
Each Lng is a carbon-carbon single bond, an ether bond, a sulfide bond, a polysulfide bond having 2 to 6 sulfur atoms, a sulfinyl bond, a sulfonyl bond, a lower alkylene bond, a di(lower alkyl)methylene bond, a lower alkylene ether bond, a crosslinking bond selected from the group consisting of a lower alkylene sulfide bond, a lower alkylene polysulfide bond, an amino bond, and a combination thereof; Q is a lower alkyl group, a lower alkoxy group, a nitro group, or a halo group; The aminophenol according to claim 8, wherein is an aromatic nucleus represented by 0 to 3). The aminophenol according to claim 1, wherein 11 Ar is a benzene nucleus having 0 to 3 substituents, and each of a, b and c is 1. The aminophenol according to claim 4, wherein 12R is a group derived from a homopolymer or interpolymer of _C2 - _C101 -olefin. 13 1-olefin is ethylene, propylene,
Aminophenol according to claim 12, which is selected from the group consisting of butylene and mixtures thereof. 14 formula (wherein R is a substantially saturated hydrocarbon group having an average of about 30 to about 750 aliphatic carbon atoms located in the ortho or para position of the hydroxyl group;
R' is a group selected from the group consisting of a lower alkyl group, a lower alkoxy group, a nitro group and a halo group, z is 0 or 1, and R is located at the ortho or para position of the hydroxyl group; The aminophenol according to claim 1, which is represented by 15. The aminophenol of claim 14, wherein 15 R has at least about 50 aliphatic carbon atoms. 15. The aminophenol of claim 14, wherein 16R is a substantially saturated pure aliphatic group. 17. The aminophenol according to claim 16, wherein 17R is located at the para position of the hydroxyl group and z is 0. 18. The aminophenol according to claim 17, wherein 18R is an alkyl group or an alkenyl group. 19. The aminophenol of claim 18, wherein 19 R has at least about 50 aliphatic carbon atoms. 15. The aminophenol according to claim 14, wherein 20 R is a group derived from a homopolymer or interpolymer of _C2 to _C10 olefins. 21. The aminophenol of claim 20, wherein the _C2 - _C10 olefin is selected from the group consisting of _C2 - _C101 -olefins and mixtures thereof. 22 1-olefin is ethylene, propylene,
Aminophenol according to claim 21, which is selected from the group consisting of butylene and mixtures thereof. 23 formula (wherein R is a substantially saturated hydrocarbon group having about 30 to about 750 aliphatic carbon atoms derived from a _C2 - _C101 -olefin homopolymer or interpolymer; The aminophenol according to claim 1, wherein R' is a group selected from the group consisting of a lower alkyl group, a lower alkoxy group, a nitro group, and a halo group, and z is 0 or 1). 24 1-olefin is ethylene, propylene,
24. The aminophenol of claim 23, which is selected from the group consisting of butylene and mixtures thereof. 25. The aminophenol of claim 24, wherein 25R is derived from a polymer of isobutene. 26. The aminophenol of claim 25, wherein 26 R is an alkyl or alkenyl group having an average of at least about 50 aliphatic carbon atoms. 27. The aminophenol according to claim 26, wherein z is 0.