CA1096886A

CA1096886A - Amino phenols useful as additives for fuels and lubricants

Info

Publication number: CA1096886A
Application number: CA263,210A
Authority: CA
Inventors: Richard M. Lange
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1975-10-14
Filing date: 1976-10-13
Publication date: 1981-03-03
Also published as: FI62555C; FI62555B; SE7611382L; AU512423B2; BE847218A; BE847219A; JPS627184B2; SE423402B; MX147153A; SE7611381L; AU1859676A; FR2327982A1; DK153141B; DE2646241A1; JPS5248638A; DK461676A; IT1121681B; FI762916A; DK160208C; FI63054C

Abstract

ABSTRACT OF THE DISCLOSURE
Amino phenols of the general formula

Description

1~68136 Background of the Invention ~1) Field of the Invention This invention relates to additive compositions for use in lubricants based on oils of lubricating viscosity and normally liquid fuels. More particularly, it relates to amino phenols having at least one hydrocarbon-based group of - at least about 10 aliphatic carbon atoms.
~2) Prior Art U.S. Patent 2,1~7,835 describes the formation of metal salts of aromatic amines, said amines being formed by nitration followed by reduction of wax-substituted, hydroxy-- aromatic hydrocarbons. These metal salts can be incorpor-- ated in mineral oils to depress their pour points and increase theix viscosity indices.
15 ~ U.S. Patents 2,502,708 and 2,571,092 both disclose the ~ ~. . . . .
nitration and subsequent hydrogenation to an amine of cardanol. This amino cardanol is said to be useful as an . .
- anti-oxidant for mineral oils, fats and petroleum oils.
~- Cardanol, also known a-s anacardol, is also said to be a mixture of 3-pentadecylphenol, 3-(8'-pentadecenyl)phenol, 3-~8'~ pentadecadienyl)phenol and 3-(8:11:14'-pentadeca-trienyl)phenol. Formulae presented in both the '092 and -~ '708 Patents as well as the chemical literature tsee the .
Dictionary of Organic Compounds, Vol. 1, Oxford University Press, N.Y., 1965, page 229) ~how that the Cl 5 substituent in cardanol is meta to the hydroxy group.
U.S. Patent 2,859,251 discloses the alkylation of ~ ortho-, para-, and meta-amino phenols with olefin polymers ; ~ having from 6 to 18 carbon atoms per molecule in the pre-30 - sence of a catalytic complex formed by mixing hydrogen 10~6886 .. .
fluoride with boron trifluoride and an iron group metal fluoride. The '251 patent fails to disclose whether the alkyl groups in the product mixture are bonded to carbon, - nitrogen, and/or oxygen atom.
(3) General Background The improvement of the performance characteristics of lubricants based on oils of lubricating viscosity (e.g., oils and greases) and normally liquid fuels through the use of additives has been known for several decades. Still, in these days of growing material shortages, spiralling equip-ment replacement costs, increasing fuPl and lubricant costs, and environment~l consciousness, the search for new, effec-tive, alternate lubricant and fuel additives continues unabated.
(4) Objects ;
- ~herefore, it is an object of this invention to provide novel additive compositions that will impart useful and . desirable properties to oil-based lubricants and normally liqu;d fuels containing said additive compositions.
lt is a further object of this invention to provide novel concentrates and lubricants and fuels containing the amino phenols of this invention.
Other objects will be apparent to those skilled in the art upon review of the present specification.
~ummary of the In~ention ~his invention comprises amino phenols of the formula ( I C
(R)a ~ Ar (NH2)b Formula I
wherein R is a substantially saturated hydrocarbon-based ~ubstituent of at least 10 aliphatic carbon atoms; a, b, and - : , , , 1~6~86 c are each independently ~n integer of 1 up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b, and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo, or combinations of two or more of said optional substituents;
- with the proviso that when Ar is a benzene nucleus having only one hydroxyl and one R substituent, the R substituent 1~ is ortho or para to said hydroxyl substituent.
- ~ The term "phenol" is used in this specification in its art-accepted generic sense to refer to hydroxy-aromatic com-pounds having at least one hydroxyl group bonded directly to a carbon of an aromatic ring.
Lubricants based on oils of lubricating viscosity, normally liquid fuels and additive concentrates containing the above-descri~ed amino phenols are also embodiments of : this invention.
., ~ .
.. ....
~escription of *he Invention .. .. .
~he aromatic moiet~, Ar.
The aromatic moiety, Ar, can be a single aromatic nucleus such as a benzene nucleus, a pyridine nucleus, a thiophene nucleus, a 1,2,3,4-tetrahydronaphthalene nucleus, etc., or a polynuclear aromatic moiety. Such polynuclear moieties can be of the fused type; that is, wherein at least two aromatic nuclei are fused at two points to another nucleus such as found in naphthalene, anthracene, the azanaphthalenes, etc. Such polynuclear aromatic moieties also can be of the linked type wherein at least two nuclei , ~ .

lQ~6~

(either mono or polynuclear) are linked through bridging linkages to each other. Such bridging linkages can be chosen from the group consisting of carbon-to-carbon single bonds, ether linkages, keto linkages, sulfide linkages, polysulfide linkages of 2 to 6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, methylene linkages, alkylene linkages, di-(lower alkyl)methylene linkages, lower alkylene ether linkages, alkylene keto linkages, lower alkylene sulfur linkages, lower alkylene polysulfide linkages of 2 to 6 carbon atoms, amino linkages, polyamino linkages and mixtures of such divalent bridging linkages. In certain instances, more than one bridging linkage can be present in Ar between aromatic nuclei. For example, a fluorene nucleus has two benzene nuclei linked by both a methylene linkage ~and a covalent band. Such a nucleus may be considered to have 3 nuclei but only two of them are aromatic. Normally, Ar will contain only carbon atoms in the aromatic nuclei per se. ~ :
The number of aromatic nuclei, fused, linked or both, in Ar can play a role in determining the integer values of a, b and c in Formula I. For example, when Ar contains a æingle aromatic nucleus, a, b and c are each independently l to 3. When Ar contains 2 aromatic nuclei, a, b and c can each be an integer of l to 6, that is, up to three times the number of aromatic nuclei present (in naphthalene, 2). With a trinuclear Ar moiety, a, b and c can each be an integer of l to 9. For example, when Ar is a biphenyl moiety, a, b and c can each independently be an integer of l to 6. The values o~ a, b and c are obviously limited by the fact that their sum cannot exceed the total unsatisfied valances of 10~68~36 .. ~
The single ring aromatic nucleus which can be the Ar moiety can be represented by t.he general formula ar(Q)m wherein ar represents a single ring aromatic nucleus (e.g., S - benzene) of 4 to 10 carbons, each Q independently represents a lower alkyl group, lower alkoxy group, nitro group, or halogen atom, and m is O to 3.- As used in this specifi-cation and appended claims, "lower" refers to groups having - ~ . 7 or less carbon atoms such as lower alkyl and lower alkoxyl 10 groups. Halogen atoms include fluorine, chlorine~ bromine - and iodine atoms; usually, the halogen atoms are fluorine ~ and chlorine atoms.
: - Specific examples Of Such single ring Ar moieties are the following:
- . -.

N~CN~U N~N
. ~ -Et ~ ~
- Me~ . H ~OPr H ~ H

~ , . . - :

~ ~ ; nl~cMc N~C Cl N l¢L--N

;: - - H2 1 ~CH2- CH2 ~r~ ~ N2 ~ CU2-- CN
z

- 2 etc.
, ' ' ' . ' ' - 5 - . j 6~6 wherein Me is methyl, Et is ethyl, Pr is n-propyl, and Nit iS nitro.
When Ar is a polynuclear fused-ring aromatic moiety, it .. can be represented by the general formula ar~ ar ~ m~ ~Q)mm wherein ar, Q and m are as defined hereinabove, m' is 1 to 4 and ~ represent a pair of fusing bonds fusing two rings so as to make two carbon atoms part of the rings of each of two adjacent rings. Specific examples of fused ring aromatic ~ moieties Ar are:
-H
- H ~ H N ~
. H ~ H : ~ H

MeO
~ Me ~ ` ~ Me M ~ ~ Nit - H ~ H H ~ -H
- ~ ~ N H

~ ~ n~ MeO~\~
H~ ~ .
: . H
~tc.
When the aromatic moiety Ar is a linked polynuclear aromatic moiety it can be represented by the gener~.l formula ar~Lng-ar-tw(Q)mw wherein w is an integer of 1 to about 20, ar is as described above with the proviso that t~ere are at least 3 unsatisfied ~i.e., free) valences in the total of ar groups, Q and m are ~ 8 6 as defined hereinbefoxe, and each Lng is a bridging linkage individually chosen from the group consisting of carbon-to-carbon single bonds, ether linkages (e.g., -0-~, keto linkages (e.g., -C-), sulfide linkages (e.g., -S-), polysulfide linkages of 2 to 6 sulfur atoms (e.g., -S2-6-), sulfinyl linkages (e.g., -S(O)-~, sul-fonyl linkages (e.g., -S(0)2-), lower alkylene linkages (e.g., -CH2-, -CH2-CH2-, -CH-CH-, etc.), di(lower alkyl)-R
methylene linkages (e.g., -CRz-), lower alkylene ether - 10linkages (e.g., -CH20-, -CH20-CH2-, -CH2-CH20-, -CH2CH20CH2CH2-, -CH2lHOCH2lH_, CH2CHOIHCH2-, R R R R O

~ etc.), lower alkylene keto linkages (e.g., -CH2C-, , O
' 11 -CH2CCH2-), lower alkylene sulfide linkages (e.g., wherein one or more -O-'s in the lower alkylene ether linkages is replaced with an -S- atom), lower alkylene polysulf^de linkages (e.g., wherein one or more -O-'s is replaced with a -S2-6 group),amino linkages (e.g., -N-, -I_, -CH2N-, - H R
- -CH27CH2-, -alk-l_, where alk is lower alkylene, etc.), polyamino linkages ~e.g., -I(alk~ O, where the unsatis-fied free N valences are taken up with H atoms or R groups),and mixtures of such bridging linkages (each R being a lower alky~ group).
Specific examples of Ar when it is a linked polynuclear axomatic moiety include:

H H H H
. ,, ~_CU~

. . H2 ~5 ~ ~ 1 3 : ,et -Usually all these Ar moieties are unsubstituted except for the R, -OH and -NH~ groups (and any bridging groups).
For such reasons as cost " availability, performance, etc., the Ar moiety is normally a benzene nucleus, lower ' .

~6~386 alkylene bridged benzene nucleus, or a naphthalene nucleus.
Thus, a typical Ar moiety is a ~enzene or naphthalene nucleus having 3 to 5 unsatisfied valences, so that one or - two of said valences may be satisfied by a hydroxyl group With the remaining unsatisfied valences being, insofar as possible, either ortho or para to a hydroxyl group. Pre-' ferably, Ar is a benzene nucleus having 3 to 4 unsatisfied . valences so that one can be satisfied by a hydroxyl group with the remaining 2 or 3 being either ortho or para to the 10 hydroxyl gr~up.
.' The Substantially Satura*ed H~dxocarbon-based ~roup R.
_ The amino phenols of the present invention contain, '~ - .... directly bonded to the aromatic moiety Ar, a substantially ' saturated monovalent hydrocarbon-based group R of at least . .
about 10 aliphatic carbon atoms. This R group can have up '. - to a~out 400 aliphatic carbon atoms. More than one such . group can be present, but usually, no more than 2 or 3 such 'h~ . .groups are present for each aromatic nucleus in the aromatic ~ . .
.- m~iety Ar. The total number of R groups present is indi-.
cated by the value for "a" in Formula I. Usually, the hydrocarbon-based group has at least about 30, more typi ~ ... cally, at least about 50 aliphatic carbon atoms and up to : about 750, more typically, up to about 400, usually 300 - ~ aliphatic carbon atoms. Typically, these R groups are ,.~ 25 alkyl or alkenyl groups.
_ __ _ .. ... ... .
~:;' ~ Generally, the hydrocarbon-based groups R are made from homo- or interpolymers (e.g., copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-l, isobutene, butadiene, iso-prene, l-hexene, l-octene, etc. Typically, these olefins ar~ l-monoolefins. The R groups can also be derived from 10968~6 ~. .
the halogenated (e.g., chlorinatea or brominated) analogs of Such homo- or interpolymers. The R groups can, however, be .made from other sources, such as monomeric high molecular weight alkenes (e.g., l-tetracontene) ana chlorinated-analogs and hydrochlorinated analogs thereof, aliphatic petroleum fractions, particularly paraffin waxes and cracked and chlorinated analogs and hydrochlorinated analogs thereof, white oils, synthetic alkenes such as those produced by the -Ziegler-Natta process (e.g., poly(ethylene) greases) and io other sources known to those skilled in the art. Any un-saturation in the R groups may be reduced or eliminated by hydrogenation according to procedures known in the art before the nitration step d~scribed hereafter.
As used herein, the term "hydrocarbon-based" denotes a - 15 group having a carbon atom directly attached to the re--mainder of the molecule and having a predominantly hydro-.
carbon character within the context of this invention.
Therefore, hydrocarbon-based groups can contain up to one - non-hydrocarbon radical for every ten carbon atoms provided - 20 this non-hydrocarbon radical does not significantly alter the predominantly hydrocarbon character of the group. Those skilled in the art will be aware of such radicals, which include, for example, hydroxylj halo (especially chloro and fluoro), alkoxyl, alkyl mercapto, al~yl sulfoxy, etc.
- ~ ~5 Usually, however, the hydrocarbon-based ~roups R are purely ; hydrocarbyl and contain no such non-hydrocarbyl radicals.
The hydrocarbon-based groups R are substantially sat-urated, that is, they contain no more than one carbon-to-caxbon unsaturated bond for every ten carbon to-carbon single bonds present. Vsually, they conta~n no more than ' .

10~6886 ne carbon-to-carbon non-aromatic unsaturated bond for every 50 carbon-to-carbon bonds present.
The hydrocarbon-based groups of the amino phenols of this invention are also substantially aliphatic in nature, that is, they contain no more than one non-aliphatic moiety (cycloalkyl, cycloalkenyl or aromatic) group of six or less carbon atoms for every ten carbon atoms in the R group.
Usually, however, the R groups contain no more than one such - non-aliphatic group for every fifty carbon atoms, and in many cases, they contain no such non-aliphatic groups at all; that is, the typical R groups are purely aliphatic.
~ypically, these purely aliphatic R groups are alkyl or alkenyl qroups.
Specific examples of the substantially saturated hydrocarbon-based R groups are the following:
.
a tetra(propylene) group a deca(propylene) group a tri (isobutene) group a trideca(isobutene) group . _ . . . . .... . . ... .. __ . . . _ ~a tetracontanyl group a henpentacontanyl group -; a mixture of poly(ethylene/propylene) groups of about 35 to about 70 carbon atoms a mixture of the oxidatively or mechanically degraded poly(ethylene/propylene) groups of about 35 to about 70 carbon atoms a mixture of poly~propylene/l-hexene) groups of about 80 to about 150 carbon atoms a mixture of poly(isobutene) groups having between 20 and 32 carhon atoms a mixture of poly(isobutene) groups having an average of 50 to 75 carbon atoms Typically R groups are derived from homo- or interpolymerized C2-l0 l-olefins such as ethylene, propylene, butenes and mixtures thereof. A preferred source of the group R are poly(iso~utene)s obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75 weight percent and isobutene content of 15 to 60, typically 3G to 60, weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybu-tenes contain predominantly (greater than 80~ of total -repeat units) isobutene repeating units of the configuration CH~- C -_ _ CH3 The attachment of the hydrocarbon-based group R to the ar~matic moiety Ar of the amino phenols of this invention can be accomplished by a number of techniques well known to those skilled in the art. One particularly suitable techni-que is the Friedel-Crafts reaction, wherein an olefin ~e.g., a polymer containing an olefinic bond), or halogenated or hydrohalogenated analog thereof, is reacted with a phenol.
The reaction occurs in the presence of a Lewis acid catalyst te.g., boron trifluoride and its complexes with ethers, phenols, hydrogen fluoride, etc., aluminum chloride, aluminum - bromide, zinc dichloride, etc.). Methods and conditions for carrying out such reactions are well known to those skilled in the art~ See, for example, the discussion in the article entitled, "Alkylation of Phenols" in "Rirk-Othmer Encyclo-pedia of Chemical Technology", Second Edition, Vol. 1, pages 894-895, Interscience Publishers, a division of John Wiley and Company, N.Y., 1963. Other equally appropriate and ~onvenient techniques for attaching the hydrocarbon-based group R to the aromatic moiety Ar will occur readily to those skilled in the art.

6~386 As ~ill be appreciated from inspectio~ of Form~lla I
that the amino phenols of this invention contain at least one of each of the following substituents: a hydroxyl group, a R group as defined above, and a primary amine S group, -N~. Each of the foregoing ~roups must be attached to a carbon atom which is a part of an aromatic nucleus in the Ar moiety. They need not, however, each be attached to the same aromatic ring if more than one aromatic nucleus is present in the Ar moiety.
~ 10 In a preferred embodiment, the amino phenols of this - invention contain one each of the foregoing substituents and but a single aromatic ring, most preferably benzene. This preferred class of amino phenols can be represented by the . formula OH
~ NH2 - 15 R' t~ ~

) Z
wherein the R' group is a hydrocarbon-based group of about 30 to about 400 aliphatic carbon atoms located ortho or para to the hydroxyl qroup, R''' is a lower alkyl, lower alkoxyl, nitro group or halogen atom and z is 0 or 1~ Usually z is 0 and R' is a substantially saturated, purely aliphatic group.
O~ten it is an alkyl or alkenyl group para to the -OH sub-~tituent Another class of amino phenols of this invention is represented by the formula R ~ ~ ~ -(NH2)1-2 R~

~"6~86 wherein R is a substantially saturated hydrocarbyl substi-tuent having an average of from about 30 to about 750 ali-phatic carbon atoms; R' is a substituent selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo; and z is 0 or 1 with the proviso that R is ortho or - para to the phenolic hydroxyl group.
In a still more preferred embodiment of this invention, the amino phenol is of the formula OH
~ . : ~NH 2 : R"

wherein R" is derived from homopolymerized or interpoly-merized C2-lo l-olefins and has an average of from about 30 to about 300 aliphatic carbon atoms and R''' and z are as ~ ~ -defined above. Usually R" is derived from ethylene, pro-:~ ~ - pyl~ne, butylene and mlxtures thereof. Typically, it is i5 derived from polymerized isobutene. Often R" has at least about 50 aliphatic carbon atoms and z is 0.
Another class of amino phenols of this invention is represented by the formula . . - OH
: : . (H2N)o-1 I NH2 z~J

; ~ ~ . . R
.
~ ~ ~ 20 ~berein R is derived from homopolymerized or interpolymerized ~ ! ' C2-lo l~olefins and has an average of from about 30 to about . . 750 aliphatic carbon atoms; R' is selected from the group ~- consisting of lower alkyl, lower alkoxyl, nitro and halo;

and z is O or 1, with the proviso that when there is only one amino group ortho to the phenolic hydroxyl group, then R', if present, can be ortho to said hydroxyl group~ In this émbodiment, R often contains an average of at least 50 aliphatic carbon atoms and is made from homo- and inter-polymers of ethylene, propylene, butenes and mixtures thereof.
R groups derived from polymerized isobutene are typical.

.. .. ..
- The amino phenols of the present invention can be prepared by a number of snythetic routes. These routes can vary in the type reactions used and the seqllence in which - they are employed. For example, an aromatic hydrocarbon, such as benzene, can be alkylated with alkylating agent such as a polymeric olef in to form an alkylated aromatic inter-mediate. ~his intermeaiate can then be nitratea~ for lS example, to form polynltro intermediate. The polynitro intermediate can in turn be reduced to a diamine, which can then be diazotized and reacted with water to convert one of `~ : the amino groups into a hydroxyi group and provide the desired amino phenol. Alternatively, one of the nitro groups in the polynitro intermediate can be converted to a hydroxyl group through fusion with caustic to provide a hydroxy-nitro alkylated aromatic which can then be reduced to provide the desired amino phenol.
Another useful route to the amino phenols of this invention involves the alkylation of a phenol with an ole-finic alkylating agent to form an alkylated phenol. This alkylated phenol can then be nitrated to form an inter-mediate nitro phenol which can be converted to the desired amino phenols and by reducing at least some of the nitro groups to amino groups.

~ 15 ~

. ~3!968~36 ~echniqu~s for alk~l~ting.phenols are wcll knot~n to ~hose skillcd in the art as the above-no~ed article in Kirk-Othmer "Encyclopedia of Chemical Technolog~" demonstrates.
Techniques or nitrating phenols are also ~nown. See, ~or S example, in Kirk-Othmer "Encyclop~dia of Chemical Technolo~y", Second Edition, Vol. 13, the article entitled "Nitrophenols", . page 888 et seq., as well as ~he trea~ises "Axomatic Substi-- .tu~ion; N;tration and Halogenation" by P. B. D. De La Mare and . .
J. l~. Ridd, N. Y., Academic Press, 1959; "Nitration and Aro-~ ; 10 matic Reactivity" by J. G. Hogget, London, Cambridge Univer-.. ... sity Press, 1961; and "~he ~hemistry of the Nitro and .: i - ; Nitroso Groups", Henry Feuer, Editor, Intersc~ence Pub--~ ~ . - lishers, N.~., 1969. --. . Aromatic hydroxy compounds can be nitrated ~ith nitric acid, mixtures of nitric acid with acids such as sulfuric .. . .......................................... ..
. . : acid or boron trifluoride, nitrogen tetraoxide, nitronium .~ - ;. tetrafluoroborates and acyl nitrates. Generally, nitric acid ;.--- : of a concentration of, for example, about 30-90, often about 60-: . . .
~~ ~ - 90% is a convenient nitrating reagent. Substantially inert liquid . .
diluents and solvents such as ace~ic or butyxic acid can aid . in carrying out the reaction by improving reagent con~ac~.
.. . ~ Conditions and concentrations or nitrating hydroxy -aromatic compounds are also well known in the art. For , example, ~he reaction can be carried out at temperatures o~
about -15~C. to about 150C. Usually nitration i.s con-~eniently caxried out betwee~ abvut 25-75C.
Generally, depending on the particular nitrating agent - ;~- about 0.5-4 moles o~ nitrating agent is used ~ox every mole ~: o aromatic nucleus present in the hydroxy aromatic inter-mcdiate to be nitrated. ~ more than one aromatic nucleus is ;, .
~ 5 ~ .

, ...... . . . .... . ... . . .. . .. .. . . . . . .

1~"6886 present in the Ar moiet~, the amount of nitrating agent can be increased proportionately according to the number of such nuclei present. For example, a mole of naphthalene-based aromatic intermediate ~as,for purposes of this invention, the equivalent of two "single ring" aromatic nuclei so that about 1-4 moles of nitrating agent would generally be used.
When nitric acid is used as a nitrating agent usually about 1.0 to about 3.0 moles per mole of aromatic nucleus is used.
Up to about a 5-molar excess of nitrating agent (per "single ring" aromatic nucleus) may be used when it i5 desired to drive the reaction forward or carry it out rapidly.
~- - Nitration of a hydroxy aromatic intermediate generally takes 0.25 to 24 hours, though it may be convenient to react . .
the nitration mixture for longer periods, such as 96 hours.
Reduction of aromatic nitro compounds to the corres-~-~ ponding amines is also well known. See, for example, the article entitled "Amination by-Reduction" in Kirk-Othmer Encyclopedia of Chemical Technology", Second Edition, Vol.
~2, pages 76-9~. Generally, such reductions can ~e carried out with, for example, hydrogen, carbon monoxide or hydra-. - - zine, (~r mixtures of same) in the presence of metallic catalysts such as palladium, platinum and its oxides, nickel, copper chromite, eto. Co-catalysts such as alkali or alkaline earth metal hydroxides or amines (including a~ino phenols) can be used in these catalyzed reductions.
Reduction can also be accomplished through the use of reducing metals in the presence of acids, such as hydro-chloric a¢id. Typical reducing metals are æinc, iron and ti~, salts of these metals can also be used.

, ~ 6~386 ~ ..
Nitro groups can also be reduced in the Zinin reaction, which is discussed in "Organic Reactions", Vol. 20, Jo~n Wiley ~ Sons, N.Y., 1973, page 455 et seq. Generally, the Zinin reaction involves reduction of a nitro group with divalent negative sulfur compounds, such as alkali metal sulfides, polysulfides and hydrosulfides.
The nitro groups can be reduced by electrolytic action;
~ee, for example, the "Amination by Reduction" article, - ` - referred to above.
Typically the amino phenols of this invention are obtained by reduction of nitro phenols with hydrogen in the p~esence of a metallic catalyst such as discussed above.
This reduction is generally carried out at temperatures of about 15-250C., typically, about 50-150C., and hydrogen - 15 pressures of about 0-2000 psig, typically, about 50-250 psig. The reaction time for reduction usually vaxies between about 0.5-50 hours. Substantially inert liquid diluents and solvents, such as ethanol, cyclohexane, etc., ~ can be used to facilitate the reaction. The amino phenol product is obtained by well-known techniques such as dis-- tillation, filtration, extraction, and so forth.
The reduction is carried out until at leas~ about 50%, usually about 80%, of the nitro groups present in the nitro intermediate mixture are converted to amino groups. The typical route to the amino phenols of this invention just described can be summarized as (I) ni~rating with at least one nîtrating agent at least one compound of the form~la ~OH) c (R)a Ar' a6886 wherein R is a substantially saturated hydrocarbon-based group of at least 10 aliphatic carbon atoms; a and c are çach independently an integer of 1 up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar'; and Ar' is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo, or combinations - - of two or more optional substituents, with the provisos that ta~ Ar' has at least one hydrogen atom directly bonded to a carbon atom which is part of an aromatic nucleus, and (b~
when Ar!is a benzene having only one hydroxyl and one R
substituent, the R substituent is ortho or para to said hydroxyl substituent, to form a first reaction mixture : 15 containing a nitro intermediate, and (II~ reducing at least -about 50~ of the nitro groups in said first reaction mixture . to amino groups.
`. Usually this means reducing at least about 50% of the nitro groups to amino groups in a compound or mixture of compounds of the formula H)C
~ R)~ Ar (NO2)b wherein R is a substantially saturated hydrocarbon-based ~ubstituent of at least 10 aliphatic carbon atoms; a, b and c are each independently an integer of 1 up to three times the number of aromatic nuclei present in Ar with the pro-viso that the sum of a, b and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic moiety having O to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, halo, or combina-~ - 18 -~68~6 tions of two or more of said optional substituents; with the proviso that when Ar is a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is ortho or para to said hydroxyl substituent.
~nother typical route to certain amino phenols of this invention can be summarized as (I) nitrating with at least one nitxating agent at least one compound of the formula OH

R - ~ (R')z wherein R is a substantially saturated hydrocarbyl group of about 30 to about 750 aliphatic carbon atoms; R' is a substi-tuent selected from the group consisting of lower alkyl, lower alkoxyl, nitro and halo; z is 0 or 1; to form a first reaction mixture containing a nitro intermediate, and (II) reducing at least about 50% of the nitro groups in said first reaction mixture to amino groups. Usually the nitrating agent is nitric acid and the reduction is carried out with hydrogen in the presence of a metallic hydrogenation catalyst. The R group is ortho or para to the phenolic hy-droxyl group.
The following examples demonstrate the practice of the present invention in some of its various aspects. All parts and percentages in the examples and elsewhere in the specifi-cation and claims are by weight and likewise, all temperatures are in degrees centrigrade (C.), unless expressly stated to the contrary.

~ 19 -1[3"6~36 Example lA
.
To a mixture of 361.2 parts of a tetrapropenyl-suh~
stituted phenol and 270.9 parts of glacial acetic acid, at 7-17, is added a mixture of 90.3 parts of nitric acid (70-71% HN03) and 90.3 parts of glacial acetic aci~. The addi-tion is carried out over 1.5 hours while the reaction mix-ture is cooled externally to keep it at 7-17. The cooling bath is removed and the reaction stirred for 2 hours at room temperature. The reaction is then stripped at 134/35 tor _ 10 ~ and filtered to provide the desired nitrated intermediate as a filtrate having a nitrogen content of 4.65%.
Example lB
, A mixture of 150 parts of the product of lA and 50 parts of ethanol is added to an autoclave. This mixture is 15 -` degassed by purging with nitrogen and 0.75 part of palla-dium on charcoal catalyst is added. The autoclave is evacu-ated and pressured with nitrogen several times and then put - -under a hydrogen pressure of 100 psig. The reaction mixture is ~ept at 95 to lQ0 for 2.5 hours while the hydrogen - pressure varies from 100 to 20 p5ig. As the hydrogen , .. .. ,. ... ,~ ~ _ 0~6886 pressure drops below 30 psig, it is adjusted back to loO
psiq. The reaction is continued for 2Q.5 hours at which polnt the autoclave is reopened and an additional 0.5 part of palladium on charcoal catalyst added. After repeated nitrogen purging (3 times) the autoclave is again pressured to 100 psig with hydrogen and the reaction continued for an additional 16.5 hours. A total of 1.63 moles of hydrogen is fed to the autoclave. The reaction mixture is filtered and stripped to 130/16 tor. A second filtration provides the product which has the nitroge~ content of 4.78~.
Exa~ple 2A

.
To a mixture of 3,685 parts of a p~lyisobutene-sub-stituted phenol (wherein the polyisobutene substituent - contains 22 to 25 carbon atoms~ and 1,400 parts of textile spirits iS added 790 parts of nitric acid (70%~. The reaction temperature is kept below 50. After being stirred for about 0.7 hour, the xeaction mixture is poured into 5,000 parts of ice and stored ~or 16 hours. The organic layer which separates is washed twice with water and then combined with 1,000 parts of benzene. This solution is ~tripped to 170 and the residue filtered to provide the desired intermediate having a nitxogen content of 2~41% and a viscosity at 99 of 150.8 SUS.
Example 2B
__ .
A mixture of 130 parts of the product of 2A, 130 parts of ethanol, and 0.2 part of platinum oxide ~PtO2) is charged to a hydrogenation bomb. The bomb is purged several times with hydrogen and then charged to 54 psig with hydro-gen. The bomb is rocked for 24 hours and again charged to 70 psig with hydrogen. Rocking is continued for an addi--- ~0 --~6886 tional 98 hours. Stripping of the resulting reaction mix-ture to 145/760 tor provides the desixed product.
Exa~ple 2C
A mixture of 420 parts of the product of 2A, 326 parts of ethanol and 12 parts of commercial nickel on kieselguhr catalyst is charged to an appropriately sized hydrogenation bomb. The bomb is pressured to 1,480 psig with hydrogen and agitated for 5.25 hours. The resultant reaction mixture is stripped to 65C./30 tor to provlde the product as a residue having a nitrogen content of 2.62%.
.... .. .. .
Exa~ple 2D
A mixture of 105 parts of the product of 2A, 303 parts cyclohexane and 4 parts commercial Raney nickel catalyst is ~charged to an appropriately sized hydrogenation bomb. The - 15 bomb is pressured to 1,000 psig with hydrogen and agitated at about 50 for 16 hours. The bomb is again pressured to 1,100 pslg and agitated for another 24 hours. The bomb is ~- then opened and the reaction mixture filtered and recharged -~ . to the bomb with a fresh portion of 4 parts of Raney nickel catalyst. The bomb is pressured to 1,100 psig and agitated for 24 hours. The resultant reaction mixture is stripped to 95/28 tor to provide the product having a hydroxyl content of 5.24~ and a nitrogen content of 2.25%.
Example 3A
An alkylated phenol is prepared by reacting phenol with polyisobutene having a number average molecular weight of approximately 1000 (vapor phase osmometry) in the presence of a boron trifluoride phenol,complex catalyst. Stripping of the product thus formed first to 230/760 tor (vapor ~q~968 !36 ~ .
temperature) and then to 205 vapor temperature/50 tor provides purified alkylated phenol.
To a mixture of 265 parts of purified alkyl phenol, 176 parts blend oil and 42 parts of a petroleum naphtha having a boiling point of approximately 20 is added slowly 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, stripped to 120/20 tor and fil-tered to provide an oil solution of the desired nitro phenol intermediate.
Exa~ple 3B
- A mixture of 1,500 parts of the product solution of 3A, 642 parts of isopropanol and 7.5 parts of nickel on kiesel-guhr catalyst is charged to an autoclave under a nitrogen atmosphere. After purging and evacuation with nitrogen 3 times, the autoclave is pressured to 100 psig with hydrogen - and stirring is begun. The reaction mixture is held at 96 for a total of 14.5 hours while a total of 1.66 moles of hydrogen is fed to it. After purging with nitrogen 3 times the reaction mixture is filtered and the filtrate stripped to 120/18 tor. Filtration provides the desired product in an oil solution containing 0.54~ nitrogen.
~xample 4A
- To a mixture of 400 parts of polyisobutene-substituted phenol (wherein the polyisobutene substituent contains approximately 100 carbon atoms), 125 parts of ~extile ~pirits and 266 parts of a diluent mineral oil at 28 is slowly added 22.83 parts of nitric acid (70%~ in 50 parts of water over a period of 0.33 hour. The mixture is stirred at 28-34 for 2 hours and stripped to 158/30 tor, fil ~ 688~i tration provides an oil solution (40~) of the desired intermediate having a nitrogen content of 0.88%.
'Exampl-e 4B

. . .
' A mixture of 93 parts of the product solution of Example 4A and 93 parts of a mixture of toluene and iso-propanol (50/50 by weight) is charged to an appropriately sized hydrogenation vessel. The mixture is degassed and ,nitro~en purged; 0.31 part of a commercial pl'atinum oxide catalyst(86.4% PtO2) is added. 'The reaction vessel is pressured to 57 psig and held at 50-60 for 21 hours. A
total of 0.6 mole of hydrogen is fed to the reaction ' , vessel. The reaction mixture is then filtered and the - filtrate stripped to yield the desired product in an oil ' ~olution containing 0.44~ nitrogen.
' - 15 Exa~-ple 5A
- , ' A mixture of 2,160 parts of the polyisobutene-sub-.
stit~ted phenol of Example 4A and 1,440 parts of a diluent ~,' mineral oil is heated to 60. Then 25 parts of parafor-' '~maldehyde is added to the mixture followed by 15 parts of ; 20 aqueous hydrochloric acid. The mixture is heated to 115 for 1 hour. After storage for 16 hours at xoom temperature , the reaction mixture is heated to 160 for 1 hour while 20 ~:
parts of distillate are removed. Stripping of the reaction mixture to 160/15 tor provides an oil solution of the ~5 desired methylene-linked, polyisobutene-substituted phenol.
, Example SB

To 2,406 parts of the oil solution described in Example 5A and 600 parts of textile spirits is added 90 parts nitric ,~ acid (70%) over 1.5'hours. The reaction mixture is stirred _ 23 -. . .

- .
, ~0"68~36 for 1.5 hours, stored for 63 hours at room temperature and then heated for 8 hours at 90. Stripping to 160/18 ior provides an oil solution of the desired nitrated inter-mediate containing 0.79~ nitrogen.
Example 5C
A mixture of 800 parts of the oil solution of Example 5B and 720 parts of a toluene/isopropyl mixture (60/40 by weight) is charged to an autoclave. After nitrogen purging,

4 parts of nickel on kiesel~uhr catalyst is added. Nitrogen purging is repeated 3 times and the autoclave pressured with hydrogen to 60 psig at 25. The reaction temperature is ~ ~ slowly increased to 96 and the pressure maintained at 100 - psig for 5.5 hours. The autoclave is then opened and an additional 4 parts of nickel on kieselguhr catalyst added.
The autoclave is repressured to 100 psig hydrogen and held ~ ~ .
at 96 and 100 psig for 6 hours. The autoclave is cooled and reopened; an additional 0.8 part of platinum oxide catalyst added. The autoclave is then repressured to 90 psig with hydrogen and kept at this pressure for 8 more ~20 hours. The reaction mixture is filtered and the filtrate ~tripped to 150/18 tor to provide an oil solution of the product having a nitrogen content of 0.41%.
Example 6A
~s ` A mixture of 1,962 parts of the polyisobutene-sub-stituted phenol of Example 3A, 49.5 parts of paraformalde-~hyde, 15 parts of aqueous hydrochloric acid and 1,372 parts of diluent mineral oil is heated for 7 hours at 115. The reaction temperature is then increased to 160-165 and held there for an additional 7 hours. Four hundred parts of textile spirits is added to the mixture and it is cooled to 2~

11~3"681~6 30. Then 136.95 parts of nitric acid (70~) in 140 parts of water is ~lowly added. The reaction mixture is stirred for 1.5 hours at 30-35 and then stripped to l70D/28 tor to provide an oil solution of the intermediate which is clari-fied by filtration.
Exam~le 6B
. .
- Ninety-six parts of the oil solution described in Example 6A and 96 parts of a toluene/isopropyl alcohol mixture (50/50 by weight) is charged to an appropriately sized hydrogenation vessel. After nitrogen purging 0.32 part~of platinum oxide catalyst is added. After again purging the - ~ reaction vessel, it was pressured to 157 psig at 25 with - ~ hydrogen. The hydrogen pressure is kept between 57 and 50 . psig for 60 hours while reaction mixture is heated to 50 to -~ 15 60. The resultant reaction mixt~re is filtered and strip-ped to provide an oil solution of the product having a nitrogen content of 0.353%.
Exa~le 7A
To a mixture of 654 parts of the polyisobutene-sub-stituted phenol of Example 3A and 654 parts of iso~utyricacid at 27 to 31, is added 90 parts of 16 molar nitric acid over a period of 0.5 hour. The reaction mixture is held at 50 for 3 hours and then stored at room temperature for 63 hours~ Stripping to 160/26 tor and filtration through filter aid provides the desired nitro intermediate which has a nitroge~ content of 1.8%.
.. ..
Example- 7B
The nitro product of Example 7A is hydrogenated using a nic~el on kieselguhr catalyst following essentially the same procedure described in Example 3B.

.
~ - 25 -:1~968~6 ~xample 8A
A mixture of 4,578 parts of the polyisobutene-sub-stituted phenol of Example 3A, 3,052 parts of diluent mineral oil and 725 parts of textile spirits is heated to 60 to achieve homogenity. After cooling to 30, 319.5 parts of 16 molar nitric acid in 600 parts of water is added to the mixture. Cooling is necessary to keep the mixture below 40. After stirring the reaction mixture for an - adaitional 2 hours, 3,710 parts is transferred to a second - lO reaction vessel. This 3710 parts is treated with an addi ~ional 127.82 parts of 16 molar nitric acid in 130 parts of ~ water at 25-30, The reaction mixture is stirred for 1.5 - hours and then stripped to 220/30 tor. Filtration provides an oil solution of the intermediate.
.. . .
EXample -8B
- The oil solution of the product formed in ~xample 8A is hydrogenated using a platinum oxide catalyst in substan-- tially the same fashion as described in Example 2B to pro-- vide a diamino phenol.
-20 Ex ple 9 A mixture of 543 parts of a dinitro C2s-alkylated phenol (prepared in essentially the same manner as described in Example 8B), 543 parts of isopropanol and 200 parts of toluene is treated at l9~C. with a total of 42 parts of gaseous ammonia over a 0.75 hour period. The reaction mixture i5 tben treated with 147 parts of gaseous H2S.
Bo$h the ammonia and hydrogen sulfide treatment are carried out by introducing the gas i~to the stirred mixture under its surface. Ammonia treatment is repeated with 82 parts of ~q68~6 gaseous ammonia followed by a final treatment with 102 parts of hydrogen sulfide. Stripping of the reaction mixture to ~0/60 tor yields a residue which is combined with 161 parts of diluent oil and stripped again to 70C./18 torr. An

- 5 additional 161 parts of diluent oil and 35 parts of filter aid are added; filtration o this mixture yields a viscous filtrate which is a 40% oil solution of the desired diamino - phenol.
- The nitrations in examples 10-16 are carried out in essentially the same manner described in Example lA, using the hydroxy aromatic compounds and amounts of nitric acid . indicated in Table A. Reduction of the nitro intermediates ~ in these examples is carried out using the technique des-- cribed in the examples indicated in Table A.
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~L096886 Example 17 To a mixture of 1,056 parts of tetrapropyl-substituted phenol and 792 parts acetic acid cooled to -9 is added a mixture of 282 parts concentrated nitric acid and 264 parts acetic acid. The reaction mixture is stirred at 8-27 for 5 hours; external cooling is required to keep the reaction temperature within this range. The reaction mixture is stripped to 132/36 tor and the residue filtered to provide the desired nitro intermediate.
Exa~nple 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 quickly added 423 parts of comrnercial sodium æulfide. The cooling bath is used to keep the reaction temperature below about 65. After stirring for appro-ximately 1 hour, the reaction mixture is refluxed for 4 hours. The reaction mixture is then blown with carbon dioxide at 45-30 fox 3 hours; 500 parts of petroleum naphtha is added to the mixture and it is stirred for 16 hours. After addition of 500 parts of toluene, the reaction mixture is extracted with 500 parts of water. This ex-traction is repeated 4 times and the combined water extracts back-extracted with a mixture of petroleum naptha and toluene. The organic extracts are combined and stripped to - 25 provide a residue which is combined with 409 parts of blend oil. The combined mixture is then stripped to 105/15 tor to provide an oil solution of the desired amino phenol.
As previously indicated, the amino phenols of this invention are useful as additives in preparing lubricant compositions where they function primarily as detergents and - 29 ~

~(~9~8~;

dispersants. They are particularly useful where the oil is subjected to high temperature environments or to cyclic stresses such as those encountered in on-and-off engine operation.
The lubricating oil compositions of this invention are based on natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal co~bustion engines, such as automobile and truck engines, marinè and railroad diesel engines, and the like. Automatic transmissi~n fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubri-- cating oil and grease compositions can also benefit fr~m the incorporation therein of the amino phenols of the present . 15 invention.
Natural oils include animal oils and vegetable oils (e.s., castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of - ; lubricating viscosity derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., poly-butylenes, polypropylenes, propylene-isobutylene copo~ymers, chlorinated polybutylenes, etc.); poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and mixtures thereof;
alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.); poly-phenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, 688~
.
- etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide homopolymers and interpolymers and deri-S vatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These - are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxi~e, the alkyl and aryl ethers of these polyoxyalkylene polymers ~e.g~, methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropy-- lene glycol having a molecular weight of 1000-1500, etc.) or - is mono- and polycarboxylic esters thereof, for example, the - -- acetic acid esters, mixed C3-C~ fatty acid esters, or the - - Cl 30Xo acid diester of tetraethylene glycol.
;~ ~nother suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 10C~6886 ~ . .
the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid wi~h two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid and the like.
Esters useful as synthetic oils also include those made from C5 to C~ 2 monocarboxylic acids and polyols and polyol - ethers such as neopentyl glycol, trimethylol propane, pent- aerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class o~ synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2--~ ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-~p-tert-butylphenyl~silicate, hexyl-~4-methyl-2-pentoxy)-disiloxane, poly(methyl)siloxanes, poly(methylphenyl)silox-anes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tri-cresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these~ of the type disclosed hereinabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined .

~ ~ 32 -lOg6886 oil, Refined oils are similar to the unrefined oils except they have been further treated in one or more purification . steps to improve one or more properties. Many such puri-fication techniques are known to those of skill in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes,similar to those used to obtain refined oils,applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent addi-- tives and oil bxeakdown products.
In general, about 0.05-30, usually about 0.1-15 parts (by weight) of at least one amino phenol of this invention i~ dissolved or stably dispersed in 100- parts of oil to produce a satisfactory lubricant. The invention also con-templates the use of other additives in combination with the composition of this invention. Such additives include, for example, auxiliary detergents and dispersants of the ash-producing or ashless type, oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color ~tabilizers and anti-foam agents.
The amino phenols of this invention can also be used in fuels where they function as detergent dispersants, anti-oxidants and anti-corrosion agents. Fuel compositions of this invention usually contain a major portion of a normally li~uid fuel such as hydrocarbonaceous petroleum distillate fuel (e.g., motor gasoline as defined by ASTM Specification D-439-73 and diesel fuel or fuel oil as defined by ASTM
Specification D-396). Normally liquid fuel compositions ~6886 comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) - are:also within the scope of this invention as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale and coal. Normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuels and one - or more non-hydrocarbonaceous materials are also contem-plated. Examples of such mixtu~eS are combinations of gasoline and ethanol, diesel fuel and ether, gasoline and - nitromethane, etc. Particularly preferred is gasoline, that is, a mixture of hydrocarbons having an ASTM boiling point of 60C. at the 10% distillation point to about 205C. at the 90% distillation point.
Generally, these fuel compositions contain an amount of at least one amino phenol of this invention sufficient to impart anti-oxidant and/or dispersant and detergent pro-perties to the fuel; u.sually this amount is about 1 to about -- 10,000, preferably 4 to 1,000, parts by weight of the reac-tion product per million parts by weight of fuel. The -- preferred gasoline-based fuel compositions generally exhibit excellent engine oil sludge dispersancy and detergency . properties. In addition, they resist oxidation.
The fuel compositions of this invention can contain, in addition to the compositions of this invention, other addi-tives which are well known to those of skill in the art.
These can include anti-knock agents such as tetra-alkyl lead compounds, lead scavengers such as halo-alkanes (e.g., ethylene dichloride and ethyléne dibromide), deposit pre-ventors or modifiers such as triaryl phosphates; dyes, 10"6886 cetane improvers, anti-oxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors, such as aklylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants, anti-icing agents and the like.
In certain preferred fuel compositions of the present invention, the afore-described compositions of this invention are combined with other ashless dispersants in gasoline.
Such ashless dispersants are preferably esters of a mono- or 10 polyol and a hi~h molecular weight mono- or poly-carboxylic acid acylating agent containing at least 30 carbon atoms in the acyl moiety. Such esters are well known to those of skill in the art. See, for example, French Patent 1,396,645, sritish Patents ~81,850 and 1,055,337 and U.S. Patents 3,255,108; 3,311,558; 3,331,776; 3,346,354; 3,522,179; 3,57~,450;
3,542,680; 3,381,022; 3,639,242; 3,697,428; 3,708,522; and sritish Patent Specification 1,306,52~. Generally, the weight ratio of the compositions of this invention to the aforesaid ashless dispersants is about 0.1 to about 10.0;
preferably about 1 to about 10 parts of composition of this invention to 1 part ashless dispersant.
In still another embodiment of this invention, the inventive amino phenols can be combined with Mannich condensation products formed from substituted phenols, alde-hydes, polyamines, and amino pyridines to make lubricants and/or fuel additives. Such condensation products are described in U.S. Patents 3,649,65~; 3,558,743; 3,539,633;
3,704,308; and 3,725,277.

./' l ~
~ - 35 -l~q6886 The amino phenols of this invention can be added di-rectly to the fuel or lubricating oil to form the fuel and lubricant compositions of this invention or they can be diluted with at least one substantially inert, normally li~uid organic solvent/diluent such as mineral oil, xylene, - or a normally liquid fuel as described above, to form an additive package which is then added to the fuel or lubri-cating oil in sufficient amounts to form the inventive fuel and lubricant composition described herein. These concen-trates generally contain about 30 to about 90 percent of the composition of this invention and can contain in addition any of the above-described conventional additives, parti-cularly the afore-described ashless dispersants in the aforesaid proportions. The remainder of the concentrate is the solvent/diluent.
.

~ ~ .

, , ~ 36 -.. . . ~

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An amino phenol of the formula wherein R is a substantially saturated hydrocarbon-based substituent of at least 30 aliphatic carbon atoms; a, b, and c are each independently an integer of 1 up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b, and c does not exceed the unsatisfied valences of Ar;
and Ar is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, halo, or combinations of two or more of said optional substituents; with the proviso that when Ar is a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is ortho or para to said hydroxyl substituent.

2. An amino phenol as claimed in claim 1 wherein R has an average of up to about 750 aliphatic carbon atoms.

3. An amino phenol as claimed in claim 2 wherein R is a purely hydrocarbyl substituent.

4. An amino phenol as claimed in claim 3 wherein R is alkyl or alkenyl.

5. An amino phenol as claimed in claim 1 wherein R is made from homopolymerized or interpolymerized C2-10 olefins.

6. An amino phenol as claimed in claim 5 wherein said C2-10 olefins are selected from the group consisting of C2-10 l-olefins and mixtures thereof.

7. An amino phenol as claimed in claim 6 wherein said l-olefins are selected from the group consisting of ethylene, propylene, butylenes, and mixtures thereof.

8. An amino phenol as claimed in claim 1 wherein Ar contains two or more linked and/or fused polynuclear aromatic nuclei.

9. An amino phenol as claimed in claim 8 wherein Ar is a napthalene nucleus.

10. An amino phenol as claimed in claim 1 wherein Ar is a benzene nucleus having 0 to 3 of said optional substituents and a, b, and c are each 1.

11. An amino phenol as claimed in claim 4 wherein R is derived from homopolymerized or interpolymerized C2-10 l-olefins.

12. An amino phenol as claimed in claim 12 wherein said l-olefins are selected from the group consisting of ethylene, propylene, butylenes, and mixtures thereof.

13. An amino phenol of the formula wherein R' is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 750 aliphatic carbon atoms located ortho or para to the hydroxyl group;
R''' is a member selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo; and z is O or 1 with the proviso that R is ortho or para to the phenolic hydroxyl group.

14. An amino phenol as claimed in claim 13 wherein R' contains at least about 50 aliphatic carbon atoms.

15. An amino phenol as claimed in claim 13 wherein R' is a substantially saturated purely aliphatic group.

16. An amino phenol as claimed in claim 15 wherein R' is located para to the -OH substituent and z is o.

17. An amino phenol as claimed in claim 16 wherein R' is an alkyl or alkenyl substituent.

18. An amino phenol as claimed in claim 17 wherein R' contains an average of at least about 50 aliphatic carbon atoms.

19. An amino phenol as claimed in claim 13 wherein R' is a substituent derived from homopolymerized or interpolymerized C2-10 olefins.

20. An amino phenol as claimed in claim 19 wherein said C2-10 olefins are selected from the group consisting of C2-10 l-olefins and mixtures thereof.

21. An amino phenol as claimed in claim 20 wherein said l-olefins are selected from the group consisting of ethylene, propylene, butylenes, and mixtures thereof.

22. An amino phenol of the formula wherein R'' is derived from homopolymerized or interpolymerized C2-10 1-olefins and has an average of from about 30 to about 750 aliphatic carbon atoms; R''' is selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo; and z is 0 or 1.

23. An amino phenol as claimed in claim 22 wherein said l-olefins are selected from the group consisting of ethylene, propylene, butylenes, and mixtures thereof.

24. An amino phenol as claimed in claim 23 wherein R'' is derived from polymerized isobutene.

25. An amino phenol as claimed in claim 24 wherein R" is an alkyl or alkenyl group containing an average of at least about 50 aliphatic carbon atoms.

26. An amino phenol as claimed in claim 25 wherein z is 0.

27. An amino-containing composition made by (I) nitrating with at least one nitrating agent at least one compound of the formula wherein R is a substantially saturated hydrocarbon-based group of at least 30 aliphatic carbon atoms; a and c are each independently an integer of 1 up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b and c does not exceed the unsatisfied valences of Ar'; and Ar' is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo, or combinations of two or more optional substituents, with the provisos that (a) Ar' has at least one hydrogen atom directly bonded to a carbon atom which is part of an aromatic nucleus, and (b) when Ar is a benzene having only one hydroxyl and one R substituent, the R
substituent is ortho or para to said hydroxyl substituent, to form a first reaction mixture containing a nitro intermediate, and (II) reducing at least about 50% of the nitro groups in said first reaction mixture to amino groups.

28. An amino-containing composition as claimed in claim 27 wherein R has an average of up to about 750 aliphatic carbon atoms.

29. An amino-containing composition as claimed in claim 27 wherein Ar' has at least one hydrogen atom directly bonded to a carbon of an aromatic ring, said carbon atom being an odd number of carbon atoms away from an aromatic carbon bearing a hydroxyl group.

30. An amino-containing composition as claimed in claim 29 wherein R has an average of up to about 300 carbon atoms.

31. An amino-containing composition as claimed in claim 30 wherein R has an average of at least about 30 carbon atoms and is derived from homopolymerized or interpolymerized C2-10 olefins.

32. An amino-containing composition as claimed in claim 31 wherein Ar' is a benzene nucleus.

33. An amino-containing composition as claimed in claim 31 wherein the nitrating agent is nitric acid.

34. An amino-containing composition as claimed in claim 33 wherein the nitro intermediate is reduced by hydrogen in the presence of a metallic hydrogenation catalyst.

35. An amino-containing composition made by (I) nitrating with a nitrating agent at least one compound of the formula wherein R' is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 750 aliphatic carbon atoms located ortho or para to the phenolic hydroxyl group; R''' is a member selected from the group consisting of lower alkyl, lower alkoxyl, nitro, and halo; and z is 0 or 1 to form a first reaction mixture containing a nitro intermediate and (II) reducing at least about 50% of the nitro groups in said first reaction mixture to amino groups.

36. An amino-containing composition as claimed in claim 35 wherein R' is para to the hydroxyl group and is derived from homopolymerized isobutylene and z is 0.

37. An amino-containing composition made by reducing at least about 50% of the nitro groups to amino groups in a compound or mixture of compounds of the formula wherein R is a substantially saturated hydrocarbon-based substituent of at least 30 aliphatic carbon atoms; a, b, and c are each independently an integer of 1 up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a, b, and c does not exceed the unsatisfied valences of Ar; and Ar is an aromatic moiety having 0 to 3 optional substituents selected from the group consisting of lower alkyl, lower alkoxyl, halo, or combinations of two or more of said optional substituents; with the proviso that when Ar is a benzene nucleus having only one hydroxyl and one R substituent, the R substituent is ortho or para to said hydroxyl substituent.

38. An amino-containing composition as claimed in claim 37 wherein at least one nitro substituent is reduced with hydrogen in the presence of a metallic hydrogenation catalyst.

39. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the amino phenol claimed in claim 1.

40. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the amino phenol claimed in claim 13.

41. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the amino phenol claimed in claim 22.

42. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the amino phenol claimed in claim 27.

43. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the amino containing composition claimed in claim 35.

44. A fuel or lubricant composition containing a major proportion of a normally liquid fuel or a lubricating oil of lubricating viscosity and a minor proportion of the amino containing composition claimed in claim 37.