Note: Descriptions are shown in the official language in which they were submitted.
- ~37~ LF-2010-Ca
OXIDATIVELY COUPLED HYDROXYAROMATIC COMPOUNDS
AND FUELS AND LUBRICANTS CONTAINING THEM
..
This invention relates to new compositions of matter suit-
able for oxidative coupling, to oxidatively coupled products
prepared from such compositions and a method for their preparation,
and to additive concentrat~s, lubricants and fuels containing
such products. More specifically, the oxidatively coupled products
of this invention are prepared from a reaction mixture comprising:
~ A) At least one hydroxyaromatic compound containing no
aliphatic substituent having more than 4 carbon atoms; and
(B) At least one hydroxyaromatic compound containing at
least one aliphatic substituent having at least about 12 carbon
atoms;
at least one position ortho to a hydroxy group in each of
reagents A and B being unsubstituted.
Metho.d~. and reagents for oxidative coupling of hydroxyaro-
matic compounds are disclosed in Taylor et al., Oxidative Coupling
of Phenols (Marcel Dekker, Inc., 1967); in Patai, The Chemistry of
the Hydroxyl Group, chapters 10 and 16 (Interscience Publishers,
1971); and in many U.S. patents including the following:
~l~l 3'~7
-- 2 --
3,306,875 3,873,627
3,630,900 3,876,709
3,631,208 3,928,355
3,772,373 3,959,2~3
3,819,579 3,970,640
In general, this reaction comprises the oxidation of hy-
droxyaromatic compounds in the presence of reagents which
promote the formation of carbon-to-carbon or carbon-to-oxygen
bonds linking aromatic rings. The precise molecular structure
of the resulting products may not be readily identifiable and
it is often most convenient to define the products in terms of
the process for their preparation.
The products of this invention are prepared by oxidative
coupling of a mixture of at least two different types of
hydroxyaromatic compounds. The first type, frequently refer-
red to herein as "reagent A", contains one or more aromatic
rings and no aliphatic substituent having more than 4 carbon
atoms. If any aliphatic substituents are present, they are
generally alkyl groups. If more than one aromatic ring is
present, the rings may be fused, linked by direct carbon-to-
carbon bonds, or linked through other atoms such as oxygen or
carbon. Compounds conkaining more than one hydroxy group
attached to the aromatic moieties are included, as are com-
pounds containing other substituents such as halogen, alkyl,
hydroxyalkyl, alkoxy or alkylthio (so long as any alkyl groups
therein contain no more than 4 carbon atoms). It is essential,
however, that the hydroxyaromatic compounds contain at least
one unsubstituted position ortho to a hydroxy group. Suitable
hydroxaromatic compounds include phenol, m-cresol, p-cresol,
p-ethylphenol, a-naphthol, ~-naphthol, 4-methyl-a-naphthol,
p-chlorophenol, o-methoxyphenol, catechol, resorcinol, hydro-
quinone, hydorxybiphenyl and bisphenol A.
~37~
A preferred subgenus of compounds useful as
reagent A has the formula
-a
(OH)a
wherein a is l or 2, usually 1; each Y is individually
hydrogen, halo, alkyl or hydroxyalkyl or haloalkyl of up to
4 carbon atoms, or alkoxy or alkylthio of up to ~ carbon
atoms; and at least one and preferably two positions ortho
to a hydroxy group are unsubstituted. Most often, up to
two Y's (preferably none) are alkyl or hydroxyalkyl radi-
cals having up to 2 carbon atoms and all others are hydro-
gen. It is also preferred that the positions adjacent to
the previously mentioned unsubstitutad ortho positions not
contain bulky substituents such as t-butyl or phenyl groups
which would tend to inhibit oxidative coupling in those
positions.
The second type of hydroxyaromatic compound, fre-
quently referred to herein as "reagent B", is in most re-
spects similar to reagent A but differs therefrom in that
its molecules contain at least one (usually only one)
aliphatic substituent ha~ing at least about 12 carbon
atoms. The aliphatic substituent may be bound to the
aromatic radical through a direct carbon-to-carbon bond or
through a hetero atom such as oxygen or sulfur; the direct
carbon-to-carbon bond is preferred.
The aliphatic substituent in reagent B is usually
substantially saturated. By "substantially saturated" is
meant that it is free of acetylenic unsaturation and has no
more than one olefinic bond for each 12 carbon atoms,
usually no more than one olefinic bond for each 25 ali-
phatic carbon atoms. It is ordinarily an aliphatic hydro-
carbon radical, but it may also contain non-aliphatic
hydrocarbon substituents such as phenyl, hydroxy, nitro,
carbalkoxy, alkoxy, cyano, halo and the like. In general,
no more than one such substituent is present for every 5
and usually for every 25 carbon atoms.
A preferred subgenus of compounds useful as
reagent B has the formula
37~ 7
..
[~ ( OH ) b
wherein b is 1 or 2, usually 1; each X is individually
hydrogen, halo, alkyl or hydroxyalkyl or haloalkyl of up to
4 carbon atoms, or alkoxy or alkylthio of up to 4 carbon
atoms, R is an aliphatic radical having at least about
12 carbon atoms; and at least one and preferably two posi-
tions ortho to a hydroxy group are unsubstituted. As will
be apparent, this subgenus of preferred compounds differs
from the subgenus preferred as reagent A in the presence of
the aliphatic raaical R. The R group is most desirably para
to the hydroxy group. Most often, up to two X's (prefer-
ably none) are alkyl or hydroxyalkyl radicals having up
to 2 carbon atoms and all others are hydrogen; also, the
preference expressed with reference to reagent A for the
absence of bulky substituents applies equally to reagent B.
Illustrative aliphatic substituents on reagent B,
and present as R in the formula for the preferred subgenus,
_ are n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chloro-
octadecyl, triacontanyl and the like. The R radical pre-
ferably contains at least about 40 carbon atoms, in which
case it is most often derived from an olefin polymer such
as polypropylene, polybutene, ethylene-propylene copolymer,
butene-isoprene copolymer and the like. These polymers
usually have a number average molecular weight between
about 500 and about lS,000, preferably between about 600
and about 5,000 and most desirably between about 800 and
about 3,000, as determined by vapor phase osmometry. Es-
pecially preferred aliphatic radicals are those derived
from polybutenes containing predominantly isobutene units.
Referring to the preferred structural formula for
component B, compounds of this type may be readily prepared
from hydroxyaromatic compounds containing no R substituents
by alkylation by known methods. The invention also con-
templates the use as reagent B of the product of a previous
oxidative coupling reaction according to the invention.
~l375~
.
--5--
The ratio of reagent A to reagent B can vary
widely; for example, about 0.1-20 moles of reagent A per
mole of reagent B. Tha preferred range is from about
0.2 to about 20 moles, most desirably ~xom about 0.33
to about 15 moles, of reagent A per mole o~ reagent B.
The oxidatively coupled products of this inven-
tion are prepared by reacting the above-described mixtures
of hydroxyaromatic compounds with an oxidative coupling
agent. Suitable oxidative coupling agents are known to
10 those skilled in the art. They include, for example,
molecular oxygen in combination with copper salts and
amines; ferric iron compounds such as potassium ferricya-
nide and ferric chloride; tetravalent lead compounds such
as lead tetraacetate and lead dioxide; peroxy compounds
15 such as hydrogen peroxide, alkyl peroxide, acyl peroxide
and persulfates; periodates; Fremy's salt; silver oxide;
nickel dioxide; halogens such as ~hlorine and bromine;
potassium permanganate and other permanganates; and mix-
tures of potassium dichromate and manganese acetate.
20 Other suitable oxidative coupling agents and methods for
their use are described in the textbooks and patents pre-
viously incorporated by reference.
For the purposes of this invention, it is pre-
ferred to use as an oxidative coupling agent molecular
25 oxygen or air in the presence of a catalyst prepared by
combining a copper salt with an amine. The amine used in
the preparation of the catalyst may be primary, secondary
or tertiary, and may be a monoamine or a polyamine. Ali-
phatic (including arylaliphatic), alicyclic and heterocy-
30 clic amine~ are preferred; these include trimethylamine,triethylamine, tripropylamine, benzyldiamylamine, ethyl-
isopropylamine, 4-pentenyldimethylamine, methyl(cyclohexyl)-
amine, octyl(chlorobenzyl)amine, methyl(phenethyl)amine,
l-ethylamino-2-phenylheptane, benzyl(dihexyl)amine, 2-
35 methyloctyldiethylamine, pyridine, pyrrole, pyrrolidine,piperidine, isoquinoline, morpholine, and substituted de-
rivatives of the above-named heterocyclic amines. Ter-
tiary amines and especially tertiary heterocyclic amines
such as the pyridines are preferred.
l3~5:17 ~ -
--6--
The copper salt component of the catalyst may be
any copper salt which forms a soluble or dispersible complex
with the amine. Suitable copper salts include cuprous and
cupric halides and sulfates. The cuprous salts, and es-
pecially cuprous chloride, are preferred.
The copper salt-amine catalyst is normally pre-
pared as a complex either prior to addition to the mixture
to be oxidatively coupled, or in situ in said mixture by
adding the copper salt and amine separately thereto. The
relative proportions of copper salt and amine in the cata-
lyst complex are known to those skilled in the art and are
disclosed, for example, in the aforementioned U.S. Patents
3,306,875; 3,630,900; 3,631,208; and 3,959,223.
Compositions suitable for oxidati~e coupling are
contemplated as one aspect of the present invention. These
compositions comprise the hydroxyaromatic compounds pre-
viously identified as reagent A and reagent B in combination
with the solid and liquid components of the oxidative
coupling agent. (Gaseous components of the oxidative
coupling agent, such as molecular oxygen, must be supplied
separately when it is desired to initiate the coupling
reaction.) These compositions may also contain a substan-
tially inert, normally li~uid organic diluent such as an
aliphatic or aromatic hydrocarbon, a chlorinated or nitra-
ted aliphatic or aromatic compound, an ether or the like.Suitable diluents include benzene, toluene, xylene, chloro-
benzene, o-dichlorobenzene, nitrobenzene, nonane, dodecane,
mineral oil, chloroform and dibutyl ether. Aromatic com-
pounds are especially preferred as diluents. It is also
within the scope of the invention to use as a diluent an
excess of the amine component of the oxidative coupling
catalyst (e.g., pyridine).
The oxidative coupling reaction may be effected by
contacting the hydroxyaromatic compounds with the oxidative
coupling agent at a temperature high enough to initiate the
reaction but not high enough to cause degradation of the
reactants or product. Normally this temperature will be
3~517
,, .
--7--
between about 20C. and about 300C., most often between
about 75C. and about 250C. In cases where the oxidative
coupling reaction is initiated at relatively low tempera-
tures, it may be desirable to store the mixture comprising
the hydroxyaromatic compounds and the oxidative coupling
agent at low temperatures, such as under refrigeration.
When the oxidative coupling agent comprises at least one
gaseous reagent such as molecular oxygen, the mixture of the
hydroxyaromatic compounds and the solid and liquid com-
ponents of the oxidative coupling agent may be stored undernormal ambient conditions until it is desired to initiate
the reaction, whereupon air or oxygen is blown through the
mixture in known manner.
The progress of the oxidative coupling reaction
may often be monitored by measuring the viscosity of the
reaction mixture, which generally increases as the reac-
tion continues. When the reaction has progressed to the
desired extent, the catalyst may be removed and the pro-
duct isolated by removal of diluents (e.g., by vacuum
- 20 stripping). If the diluent is a relatively non-volatile
material such as mineral oil, its removal may be unneces-
sary and the product may be employed in solution as an
additive for lubricants or fuels.
The preparation of the oxidatively coupled pro-
duc~s of this invention is illustrated by the followingexamples. All parts are by weight; molecular weights are
number average molecular weights and are determined by
vapor phase osmometry. Polybutenyl moieties, where used,
contain predominantly isobutene units.
Example 1
A mixture of 1,665 parts of o-dichlorobenzene,
273 parts o a p-poly~utenyl phenol (molecular weight
1200), 91 parts of phenol, 43 parts of magnesium sulfate,
71 parts of pyridine and 0.94 part of cuprous chloride is
blown beneath the surface with air for 8 hours at 140C.
The reQulting composition is cooled to room temperature,
3~ q
filtered and stripped to yield the desired oxidative
coupling product.
Example 2
A mixture of 3100 parts of o-dichlorobenzene,
48 parts of magnesium sulfate, 80 parts of pyridine and
1 part of cuprous chloride is heated to 75C. as air is
bubbled beneath the surface. A solution of 300 parts of p-
polybutenyl phenol (molecular weight 1200) and 100 parts of
phenol in 780 parts of o-dichlorobenzene is added and the
mixture is heated at 140-150C. for 13 hours as air blowing
is continued. Mineral oil, 500 parts, is added and the
solution is filtered and stripped at 210C. under vacuum to
yield an oil solution of the desired oxidative coupling
product.
, . .
Example 3
A mixture of 1300 parts of o-dichlorobenzene,
39.5 parts of pyridine, 24 parts of magnesium sulfate and
0.495 part of cuprous chloride-is heated to 70C. as air
is bubbled beneath the surface. To the mixture is added
64 parts of o-hexadecyl phenol and 3.2 parts of p-cresol.
The mixture is heated at 70C. for 4 hours a air blowing
is continued. Diatomaceous earth, 40 parts, is added and
the composition is filtered and stripped at 160C. under
vacuum. The residue i5 washed with a solution of 10 parts
of concentrated hydrochloric acid in 1000 parts of
methanol, filtered and stripped to yield the desired oxi-
dative coupling product.
a~
The procedure of Example 1 is repeated except
the air blowing period is increased from 8 hours to 18
hours.
^" 1137517
Example 5
A mixture of 910 parts of o-dichlorobenzene,
24 par~s of magnesium sulate, 40 parts of pyridine and
O.S part of cuprous chloride is heated to 75C. A solu-
tion of 100 parts of p-polybutenyl phenol (molecular weight
860) and 9.4 paxts of phenol in 390 parts of o-dichloro-
benzene is added and the mixture is heated at 140-150C.
for 7 hours as air is bubbled beneath the surface. The
mixture is filtexed and stripped at 210C. under vacuum.
Xylene, 100 parts, is added to the filtrate to yield a
xylene solution of the desired oxidative coupling product.
Example 6
The procedure of Example 2 is repeated except the
amount of phenol is increased to 200 parts.
15 Example 7
To a mixture o~ 100 parts of sodium carbonate,
400 parts of water, loO parts of ethanol and 165 parts of
potassium ferricyanide is added a mixture of 300 parts of
p-polybutenyl phenol (molecular weight 1200), 25 parts of
phenol and 325 parts of mineral oil. The mixture is heated
at 70C. under nitrogen for 2 hours. Toluene, 1000 parts,
i8 added and the solution is washed three times with water,
stripped at 210C. under vacuum and filtered to yield an
oil solution of the desired oxidative coupling product.
ExamP'le' 8
A mixture of 300 parts of p-polybutenyl phenol
~molecular weight 1200), 3100 parts of o-dichlorobenzene,
48 parts of magnesium sulfate, 80 parts of pyridine and
1 part of cuprous chloride is heated to 75C. A solution
of 100 parts of phenol in 780 parts of o-dichlorobenzene
is added over 1 hour as the mixture is blown with air; air
blowing i8 continued for 17 hours at 140-160C. Mineral
oil, 500 parts, is added and the composition is filtered
and stripped at 210C. under vacuum to yield an oil solu-
tion o the desired oxidative coupling product.
'
~ 3751~ ~
--10--
Example 9
A mixture of 510 parts of o-dichlorobenzene,
24 parts of magnesium sulfate (a drying agent used to
remove water as it is formed), 40 parts of pyridine and
1 part o~ cuprous chloride is heated to 75C. as air is
bubbled beneath the surface. A solution of 105 parts of
the oxidative coupling product of Example 6 and 25 parts
of phenol in 300 parts of o-dichlorobenzene is added and
the reaction mixture is heated at 140-150C. for 13 hours
as air blowing is continued. Mineral oil, 50 parts, is
added and the composition is filtered and stripped at
210C. under vacuum to yield a xylene solution of the
desired oxidati~e coupling product.
Example 10
The procedure of Example 9 is repeated except
the product of Example 6 is replaced with 232 parts of the
product of Example 2,-
Example 11
_ .
The procedure of Example 1 is repeated except the '~
o-dichlorobenzene is replaced with xylene on an equal
weight basis.
Examples 12-21
Oxidatively coupled compositions are prepared
from the reaction mixtures listed in the following table
accoraing to the general procedure of Example 1.
3~17
., .
.,~
.
h m
.. .. .. .. .. .. .. .. .. .. ..
,,
o~
.,.
~o
.,, s ~ ,
~X o
~-~1 tn
aJ , ~ ~
'a O h
~, s~
0
m
~1 oQI ~ ~ h ~
O ~-rl ~ ~1 0
a~: .c ~1 o :1 S o u~
O O . ~ X O ~~ O
a~ oQ-
0 ' ~ ~ ~-- Z
: C~ ~ O ~L X O ~ S; m P.
.
. O O O O O O O OO rl
. ~ o O o O U~ O ~ O
~1 ~ o a~ ~o
a~ _~
~; o
o _/
o o o ~ o o ~ o
.c a) ~o
~: ~1 0 J S ~
a) o
~>~
rl ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
l o
~ ~ a) o ~ a
q) ~ IJ ~ h ~ ~ O IJ
,, .4 o o .4 ~ la ,4 .
~ ~ C~ h
O Q,C O O O O O O O ~ 3
~ ~ O
,~
~i Q~
o _l o
X ~
~375~
-12-
As previously indicated, the oxidatively coupled
products of this lnvention are useful as additives for
lubricants, in which they function primarily as dispersants,
oxidation inhibitors and viscosity modifiers. They can be
employed in a variety of lubricants based on diverse oils
of lubricating viscosity, including natural and synthetic
lubricating oils and mixtures thereof. These lubricants
include crankcase lubricating oils for spark-ignited and
compression-ignited internal combustion engines, including
automobile and truck engines, two-cycle engines, aviation
piston engines, marine and railroad diesel engines, and the
like. They can also be used in gas engines, stationary
power engines and turbines and the like. Automatic trans-
mission fluids, transaxle lubricants, gear lubricants,
metal-working lubricants, hydraulic fluids and other lubri-
cating oil and grea~e compositions can also benefit from
the incorporation therein of the compositions of the pre-
sent invention.
Natural oils include animal oils and vegetable
oils (e.g., castor oil, lard oil) as well as liquid petro-
leum 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
halo-substituted hydrocarbon oils such as polymerized and
interpolymerized olefins le.g., polybutylenes, polypro-
pylenes, propylene-isobutylene copolymers, chlorinated poly-
butylenes, poly(l-hexenes), poly(l-octenes), poly(l-
decenes), etc. and mixtures thereof]; alkylbenzenes (e.g.,dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-
(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,
terphenyls, alkylated polyphenyls, etc.), alkylated di-
phenyl ethers and alkylated diphenyl sulfides and the
derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and
derivatives thereof where the terminal hydroxyl groups have
3l~;37~17
-13-
been modified by esterification, etherification, etc. con-
stitute another class of known synthetic lubricating oils.
These are exemplified by the oils prepared through poly-
merization of ethylene oxide or propylene oxide, the alkyl
and aryl ethers o~ 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-lO00, diethyl ether
of polypropylene glycol having a molecular weight of 1000-
lO 1500, etc.) or mono- and polycarboxylic esters thereof, for
example, the acetic acid esters, mixed C3-Ca fatty acid
esters, or the C~ 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating
oils comprises the esters of dicarboxylic acids (e.g.,
15 phthalic acid, succinic acid, alkyl succinic acids and
alkenyl succinic acids, maleic acid, azelaic acid, suberic
acid, sebacic acid, fumarlc acid, adipic acid, linoleic acid
dimer, malonic acid, alkyl malonic acids, alkenyl malonic
acids, etc.) with a variety of alcohols (e.g., butyl alco-
20 hol, 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
25 azelate, dioctyl phthalate, didecyl phthalate, dieicosyl
sebacate, the 2-ethylhexyl diester of linoleic acid dimer,
the complex ester formed by reacting one mole of sebacic
acid with two moles of tetraethylene glycol and two moles
of 2-ethylhexanoic acid, and the like.
E~ters useful as synthetic oils also include those
made from Cs to Cl 2 monocarboxylic acids and polyols and
polyol ethers such neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, poly-
35 aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili-
cate oils comprise another useful class of synthetic lubri-
cants (e.g., tetraethyl silicate, tetraisopropyl silicate,
tetra-t2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)
. '
,
~ 37~i17
.
-14-
silicate, tetra-(p-tert-butylphenyl) silicate, hexa-
(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes,
poly(methylphenyl)siloxanes, etc.). Other synthetic
lubricating oils include liquid esters of phosphorus-
containing acids (e.g., tricresyl phosphate, trioctylphosphate, diethyl ester of decylphosphonic acid, etc.),
polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-
tures of each with each other) of the type disclosed here-
10 inabove can be used in the lubricant compositions of thepresent invention. Unreined 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
15 directly from distillation or ester oil obtained directly
from an esterification process and used without further
treatment would be an unrefined 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
20 more properties. Many such purification techniques are
known to those of skill in the art such as solvent extrac-
tion, 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
25 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~ additives and oil breakdown products.
Generally, the lubricants of the present inven-
30 tion contain an amount of the composition of this invention
sufficient to provide dispersancy, oxidation inhibiting or
viscosity modifying propexties. Normally this amount will
be from about 0.05% to about 20~, preferably from about
0.1% to about 10%, of the total weight of the lubricant.
The invention also contemplates the use of other
additives in combination with the oxidative coupling pro-
ducts of this invention. Such additives include, for
~375~ ~
,. . .
--15--
example, ash-producing detergents, auxiliary ashless dis-
persants, corrosion- and oxidation-inhibiting agents, pour
point depressing agents, extreme pressure agents, color
stabilizers and anti-foam agents.
The ash-producing detergents are exemplified by
oil-soluble neutral and basic salts of alkali or alkaline
earth metals with sulfonic acids, carboxylic acids, or
organic phosphorus acids characterized by at least one
direct carbon-to-phosphorus linkage such as those prepared
10 by the treatment of an olefin polymer ~e.g., polyisobutene
having a molecular weight of 1000) with a phosphorizing
agent such as phosphorus trichloride, phosphorus hepta-
sulfide, phosphorus pentasulfiae, phosphorus trichloride
and sulfur, white phosphorus and a sulfur halide, or
15 phosphorothioic chloride. The most commonly used salts of
such acids are those of sodium, potassium, lithium, cal-
cium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal
salts wherein the metal is present in stoichiometrically
20 larger amounts than the organic acid radical. The commonly
employed methods for preparing the basic salts involve heat-
ing a mineral oil solution o~ an acid with a stoichiometric
excess of a metal neutralizing agent such as the metal
oxide, hydroxide, carbonate, bicarbonate, or sulfide at a
25 temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid
the incorporation of a large excess of metal likewise is
known. Examples of compounds useful as the promoter in-
clude phenolic substances such as phenol, naphthol, alkyl-
30 phenol, thiophenol, sulfurized alkylphenol, and condensa-
tion products of formaldehyde with a phenolic substance;
alcohols such as methanol, ~-propanol, octyl alcohol,
cellosolve, carbitol, ethylene glycol, stearyl alcohol,
35 and cyclohexyl alcohol; and amines such as aniline,
phenylenediamine, phenothiazine, phenyl-~-naphthylamine,
and dodecylamine. A particularly effective method for
preparing the basic salts comprises mixing an acid with an
3~517
-16-
excess of a basic alkaline earth metal neutralizing agent
and at least one alcohol promoter, and carbonating the
mixture at an elevated temperature such as 60-200C.
Auxiliary ashless detergents and dispersants are
so called despite the fact that, depending on its constitu-
tion, the dispersant may upon combustion yield a non-
volatile material s~ch as boric oxide or phosphorus pen-
toxide: however, it does not ordinarily contain metal and
therefore does not yield a metal-containing ash on com-
10 bustion. ~any types are known in the art, and any of themare suitable for use in the lubricants of this invention.
The ~ollowing are illustrative:
(1) Reaction products of carboxylic acids (or
derivatives thereof) containing at least about 34 and pre-
15 ferably at lèa~t about 54 carbon atoms with nitrogen-
containing compounds such as amine, organic hydroxy com-
pounds such as phenols and alcohols, and/or basic inorganic
materials. Examples of these "carboxylic dispersants1' are
described in British Patent 1,306,529 and in many U.S.
20 patents including the following:
~ 3,163,603 3,351,552 3,541,01~
3,184,474 3,381,022 3,542,678
3,215,707 3,399,141 3,542,680
3,219,666 3,415,750 3,567,637
3,271,310 3,433,744 3,574,101
3,272,746 3,444,170 3,576,743
3,281,357 3,448,048 3,630,904
3,306,908 3,448,049 3,632,~10
3,311,558 3,451,933 3,632,511
3,316,177 3,454,607 3,697,428
3f340,2al 3,467,668 3,725,441
3,341,542 3,501,405 Re 26,433
3,346,493 3,522,17g
(2) Reaction products of relatively high molecu-
35 lar weight aliphatic or alicyclic halides with amines, pre-
ferably polyalkylene polyamines. These may be character-
ized as "amine dispersants" and examples thereof are
described for example, in the following U.S. patents:
37~17 ~ -
-17-
3,275,554 3,454,555
3,438,757 3,565,804
(3) Reaction products of alkyl phenols in which
~he alkyl group contains at least about 30 carbon atoms
with aldehydes (especially formaldehyde~ and amines (es-
pecially polyalkylene polyamines), which may be charac-
terized as "Mannich dispersants". The materials described
in the following U.S. patents are illustrative:
3,413,347 3,725,480
3,697,574 3,726,882
3,725,277
(4) Products obtained by post-treating the car-
boxylic, amine or Mannich dispersants with such reagents as
urea, thiourea, carbon disulfide, aldehydes, ketones, car-
15 boxylic acids, hydrocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, pho~phorus compounds or
the like. Exemplary materials of this kind are described in
the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242
20 3,087,936 3,312,619 3,502,677 3,649,229
3,200,107 3,366,569 3,513,093 3,649,~59
3,216,936 3,367,943 3,533,945 3,658,836
3,254,025 3,373,111 3,539,633 3,697,574
3,256,185 3,403,102 3,573,010 3,702,757
25 3,278,550 3,442,808 3,579,450 3,703,536
3,280,234 3,455,83~ 3,591,598 3,704,308
3,281,428 3,455,832 3,600,372 3,708,522
(5) Interpolymers of oil-solubilizing monomers
such as decyl methacrylate, vinyl decyl ether and high
30 molecular weight olefins with monomers containing polar
substituents, e.g., aminoalkyl acrylates or acrylamides
and poly-(oxyethylene)-substituted acrylates. These may
be characterized as "polymeric dispersants" and examples
thereof are disclosed in the following U.S. patents:
3,329,658 3,666,730
3,449,250 3,687,849
3,519,565 3,702,300
, .~
37~17
- 18 -
Extreme pressure agents and corrosion- and oxidation-in-
hibiting agents are exemplified by chlorinated aliphatic
hydrocarbons such as chlorinated wax; organic sulfides and
polysulfides such as benzyl disulfide, bis(chlorobenzyl)di-
sulfide, dibutyl tetrasulfide, sulfurized methyl ester ofoleic acid, sulfurized alkylphenol, sulfurized dipentene,
and sulfurized terpene; phosphosulfurized hydrocarons such as
the reaction product of a phosphorus sulfide with turpentine
or methyl oleate; phosphorus esters including principally di-
hydrocarbon and trihydrocarbon phosphites such as dibutylphosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl-
phenyl phosphite, dipentylphenyl phosphite, tridecyl phos-
phite, distearyl phosphite, dimethyl naphthyl phosphite,
oleyl 4-pentylphenyl phosphite, polypropylene (molecular
weight 500)-substituted phenyl phosphite, diisobutyl-substi-
tuted phenyl phosphite; metal thiocarbamates, such as zinc
dioctyldithiocarbamate, and barium heptylphenyl dithiocarba-
mate; Group II metal phosphorodithioates such as zinc dicy-
clohexylphosphorodithioate, zinc dioctylphosphorodithioate,
barium di(heptylphenyl)-phosphorodithioate, cadmium dinonyl-
phosphorodithioate, and the zinc salt of a phosphorodithioic
acid produced by the reaction of phosphorus pentasulfide
with an equimolar mixture of isopropyl alcohol and n-hexyl
alcohol.
The oxidative coupling products of this invention can
also be used as dispersant and antioxidant additives in
fuels. The fuel compositions of the invention contain a ma-
jor proportion of a normally liquid fuel, ususally a hydro-
carbonaceous petroleum distillate fuel such as 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 comprising nonhydrocarbonaceous
materials such as alcohols, ethers, organo-nitro compounds
and the like (e.g., methanol,
37517
,
--19--
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. Such mixtures include combinations of gasoline and
ethanol, diesel fuel and ether, and the like. Particu-
larly preferred is gasoline, that is, a mixture of hydro-
10 carbons having an ASTM boiling point of about 60C. at the10% distillation point to about 205C. at the 90% distilla-
tion point.
Generally, these fuel compositions contain an
amount of the oxidative coupling product of this in~ention
15 sufficient to impart dispersancy and oxidation resistant
properties thereto; usually this amount is ~rom about 1
to about 10,000, preferably from about 10 to about 5000,
parts by weight of the oxidative coupling product per
million parts of fuel.
The fuel compositions of this invention can con-
tain, in addition to the oxidative coupling product, other
additives which are well known to those of skill in the art.
These can include antiknock agents such as tetra-alkyl lead
compounds, lead scavengers such as halo-alkanes (e.g.,
25 ethylene dichloride and ethylene dibromide), deposit pre-
ventors or modifiers such as triaryl phosphates, dyes,
cetane improvers, antioxidants such as 2,6-di-tertiary-
butyl-4-methylphenol, rust inhibitors such as alkylated
succinic acid~ and anhydrides, bacteriostatic agents, gum
30 inhibitors, metal deactivators, demulsifiers, upper cylin-
der lubricants, anti-icing agents and the like.
The oxidative coupling products of this invention
can be added directly to the fuel or lubricant. Prefer-
ably, however, they are diluted with a substantially inert,
35 normally li~uid organic diluent such as mineral oil,
naphtha, benzene, toluene or xylene, to form an additive
concentrate. These concentrates usually contain from about
. ~
' .AJ
1137517
-20-
20% to about 90% by weight of the oxidative coupling pro-
duct of this invention and may contain, in addition, one
or more other additives known in the art or described
hereinabove.
The following are illustrative of lubricant and
fuel compositions of this invention. All parts are by
weight unless otherwise indicated.
Composition A (Crankcase lubricant)
Mineral oil 81.45 parts
Product of Example 1 6.5 parts
Borated polybutenyl succinic anhydride-
ethylene polyamine reaction product 1 part
Sulfurizèd lower alkyl cyclohexenyl-
carboxylate 1.3 parts
Tetrapropenyl succinic acid 0.5 part
Poly-tisodecyl acrylate) 7.75 parts
Hindered phenol oxidation inhibitox 1.5 parts
Silicone anti-foam agent 0.006 par~
.
Composition B (Automatic transmission fluid)
Alkylaromatic synthetic oil 89.3 parts
Mineral oil 0.3 part
Product of Example 9 6 parts
Borated polybutenyl succinic anhydride-
ethylene polyamine reaction product 3 parts
Zinc dialkylphosphorodithioate0.5 part
Di-(lower alkyl) hydrogen phosphite 0.1 part
Sulfurized fatty oil-fatty acid-
olefin mixture O.S part
Hindered amine antioxidant 0.1 part
Ethoxylated alkylamine friction modifier 0.2 part
~ ~.37~7
-21-
Composition C (Middle distillate fuel)
Middle distillate fuel oil containing 50 parts
per million of the product of Example 3.
Composition D (Gasoline fuel)
S Gasoline containing 2 g. per gallon of lead as
tetraethyl lead and 20 parts per million of the pro-
duct of Example 5.
Composition E (Diesel fuel)
Diesel fuel oil containing 40 parts per million
of the composition o~ Example 2.
