Note: Descriptions are shown in the official language in which they were submitted.
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
- 4 -
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
11
~ 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:
386
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 --
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
6886
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
- CH3
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~
- 13 -
~"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;
- 14 -
1096886
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.
- 16 -
,
~ 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'
- 17 -
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
- 21 -
~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
- 22 -
~ 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
- 26 -
~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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~ 27 - .
~96886
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-- 28 --
~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,
- 30 -
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,
- 31 -
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
- 33 -
~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,
- 34 -
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 -
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