Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1075;~iS
Background of the Invention
(1) Field of the Invention
This invention relates to aromatic hydroxy compositions
useful as additives for lubricants based on oils of lubri-
cating viscosity and normally liquid fuels. More parti-
cularly, it relates to hydroxy aromatic compositions bearing
a substituent of at least about 50 aliphatic carbon atoms
and a methylol or substituted methylol group.
(2) Prior Art
Hydrocarbon-substituted phenols containing methylol or
substituted methylol groups are known in the art. See,
for example, U.S. Patents 3,306,938; 2,912,395; and 3,127,251
as well as British Patent Specification 634,960.
The reaction of alkyl phenols containing alkyl sub-
sti~uents o~ 400 to 5,000 molecular weight with formaldehvde
has been reported to give bis(methylol-hydroxy-alkylbenzyl)
compounds which afford detergency/dispersancy properties to
oils containing them; see for example, U.S. Patent 3,737,465.
The '465 patent also points out that many resinous phenol
formaldehyde condensation products of high molecular weight
ahd complex structure are also known.
(3) General Background
Over the past several decades, a number of additive
compositions have been developed which improve the per-
formance characteristics of lubricants and normally liquidfuels to which they are added. Still, increasingly severe
operating conditions as well as raw material shortages,
environmental consciousness and increasing costs has spurred
the search for and development of novel additives for fuels
and lubricants. Therefore, it is an object of this inven-
:~075Z65
tion to provide novel lubricant and fuel additives. A
further object is to provide novel lubricants and fuels.
A still further object is to provide novel concentrates of
such additives.
It is also an object of this invention to provide novel
intermediates for fuel and lubricant additives.
Other objects will be apparent to those skilled in the
art upon review of the present specification.
Summary of the Invention
The objects of this invention are achieved by providing
compositions comprising at least one hydroxy aromatic com-
pound having:
(a) at least one hydroxyl substituent bonded
directly to a carbon atom of an aromatic moiety,
Ar,
(b) at least one hydrocarbon-based substituent of
at least about 50 aliphatic carbon atoms and less than
about 300 carbon atoms bonded directly to a carbon atom
of the aromatic moiety, Ar, and
(c) at least one methylol or lower hydrocarbon-
based substituted methylol substituent bonded directly
to a carbon atom of the aromatic moiety Ar,
said compound not having any alkylene linkages between
carbon atoms of two aromatic nuclei. Lubricants based on
oils of lubxicating viscosity, normally liquid fuels and
additive concentrates containing the above-described compo-
sitions are also within the scope of this invention.
Detailed Description of the Invention
-
The aromatic moiety, Ar, can be a single ring nucleus
such as a benzene ring, pyridine ring, thiophene ring,
etc., or a polynuclear aromatic moiety. Such polynuclear
10752~iS
moieties can be o~ the fused type (e.g., wherein two rings
are ~fused at two points to another ring, such as found in
naphthalene, anthracene, etc.) or they can be of the linked
type, wherein individual aromatic rings (of either the mono-
or fused polynuclear type) are linked through divalentbridging linkages. Such bridging linkages can be chosen
from the group consisting of carbon-to-carbon single bonds;
ether linkages (such as -CH20CHz-); sulfide linkages (such
as -S-); polysulfide linkages of 2 to 6 sulfur atoms (such
as -S2- 6-); sulfinyl linkages (such as -S(O)-); sulfonyl
linkages (such as -S(O) 2-); lower alkylene sulfur linkages
(such as -CH2CH2 S-); lower alkylene polysulfide linkages of
2 to 6 carbon atoms (such as -CH2 S2-6 -); amino linkages
~such as -NH-); polyamino linkages (such as -(CH2CH2N) 1 - 1 o-);
and mixtures of such divalent bridging linkages. When Ar is
a linked polynuclear aromatic moiety, generally there are not
more than about 20 individual nuclei present and thus no
more than 19 linkages. As stated above, the hydroxy aromatic
compounds of this invention do not contain any alkylene
linkages (e.g., methylene, -CH2-) between aromatic rings.
When Ar is polynuclear the hydroxyl substituents, aliphatic
substituents, and methylol substituents can be bonded to
different nuclei.
Generally Ar is a ring nucleus or a fused double ring
nucleus which can be represented by the general formula Ar'
wherein Ar' is a benzene, naphthalene, X-substituted benzene
or X-substituted naphthalene nucleus, X being selected from
the group consisting of lower alkyl substituents, lower
alkoxy substituents, lower mercapto substituents, fluorine
atoms, chlorine atoms and nitro substituents. There may be
two or more X substituents per Ar' and such X substituents
1(~75;~5 ``
may be thc same or different. When such X substituents are
present in Ar' they are not present to such an extent as to
prevent attachment of at least one Cso+ hydrocarbon substi-
tuent, at least one hydroxyl substituent and at least one
methylol or substituted methylol substituent on Ar'. Usually,
no more than two X substituents are present in Ar'. Typically,
Ar' is a benzene or naphthalene nucieus not having any X
substituents.
Exemplary of Ar' nuclei are: benzene, toluene, xylene,
anisole, fluorobenzene, chlorobenzene, nitrobenzene, methoxy-
anisole, ethylbenzene, heptylmethylbenzene, methylmercapto-
benzene nuclei. A benzene nucleus is preferred because of
the ready availability of compounds providing such a nucleus.
As used in this specification, the term "lower" in
conjunction with, for example, alkyl and alkoxy, refers to
groups having 7 or less carbon atoms such as alkyl and alkoxy
groups.
The hydroxy aromatic compounds of the present invention
have at least one hydrocarbon-based substituent of at least
about 50 aliphatic carbon atoms which can be conveniently
represented by R. Generally R has less than about 300
carbon atoms and usually it has between about 70 and about
200 carbon atoms. Although R is aliphatic in nature it can
contain small amounts of carbocyclic groups (e.g., cyclo-
alkyl or aromatic), such as one group for every 20 non-
cyclic aliphatic carbons, which do not significantly alter
its aliphatic character. Usually, however, R is purely
aliphatic and contains only aliphatic carbon atoms.
As used herein, the term "hydrocarbon-based substi-
tuent" denotes a substituent having a carbon atom directly
--4--
1075'~5
bonded to the remainder of the molecule and having pre-
dominantly hydrocarbyl character within the context of this
invention. Such substituents include the following:
(1) Purely hydrocarbon substituents, that is aliphatie
(e.g., alkyl or alkenyl) substituents containing only earbon
and hydrogen.
(2) Substituted hydrocarbon substituents, that is,
those containing non-hydrocarbon radicals whieh, in the
eontext of this invention, do not alter the predominantly
hydrocarbyl eharaeter of the substituent. Those skilled in
the art wil~ be aware of suitable radieals (e.g., halo,
(especially chloro and fluoro), lower alkoxyl, lower alkyl
mercapto, nitro, sulfoxy, etc. radicals). The main hydro-
earbon chain can also contain a small number of hetero atoms
such as oxygen or sulfur in the form of ether and sulfide
linkages. In general, no more than about three radicals or
hetero atoms, and usually no more than one, will be present
for eaeh 20 earbon atoms in the hydrocarbon-based substituent.
Generally, the hydrocarbon-based substituent, R, in the
compositions of this invention are free from acetylenic
unsaturation. Ethylenic unsaturation, when present, usually
will be such that no more than one ethylenie linkage is
present for every 10 carbon-to-carbon bonds in the substi-
tuent. The substituents, R, are usually purel~ hydrocarbon
in nature and are typically saturated hydrocarbon.
Examples of the hydrocarbon-based substituents, R, are
substituents derived from the homopolymerization or inter-
polymerization of olefins such as ethylene, propylene, 1-
butene, 2-butene, isobutene, pentenes, hexenes, and similar
monoolefins up to C20. Usually C2_l0 l-monoolefins are
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used. Substituents derived from poly~ers of ethylene,
propylene, l-butene and isobutene are preferred, especially
those containin~ at least about 70 and usually not more than
about 200 aliphatic carbon atoms. An exemplary class of such
preferred polymers are those formed by Lewis Acid - catalyzed
polymerization of olefin mixtures c~ntaining predominantly
(i.e., greater than 50%) isobutene. Another preferred class
of polymers is those which contain predominantly (i.e.,
greater than 50 mole %) isobutene repeat units, i.e.,
fH3
-CH2f- repeat units.
CH3
The production of olefin polymers and halogenated and
hydrohalogenated analogs which serve as intermediates for
such R substituents is well known to those skilled in the
art; see, for example, the article entitled "Olefin-Polymers-
Higher Polyolefins" in Vol. 14, pages 309-313 of the below-
mentioned Kirk-Othmer "Encyclopedia of Chemical Technology".
These R substituents can be attached to the aromatic nuclei,
Ar, by techniques discussed hereinbelow.
The hydroxy aromatic compounds of this invention also
have at least one methylol or lower hydrocarbon-based
substituted methylol substitutent directly bonded to a
carbon of the aromatic nucleus, Ar. The lower hydrocarbon-
based substitutents have up to seven carbon atoms and can be
alkyl (e.g., methyl, ethyl, etc.), alkenyl (propenyl, etc.),
aryl (e.g., phenyl, tolyl), and alkaryl (e.g., benzyl~.
They can be represented by "hyd" and the methylol substi-
tuents thus can be represented by -CH20H (methylol),
-CHOH, and -COH. Usually the substituent is methylol it-
hyd (hyd) 2
self or an alkyl-substituted methylol or phenyl- substituted
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methylol substituent, e.g., -CHOH, -COH or -CHOH.
CH3 ( 3)2 C6H5
While the specific su~stituents of the hydroxy aromatic
compounds of this invention (i.e., the hydroxyl substituent,
hydrocarbon-based substituent, R, and the methylol substi-
tuent) can be attached to the aromatic nucleus, Ar, in any
sequence of reactions, it is generally optimal to attach them
in the order OH, R, methylol. This can be done, for
example, when Ar is a benzene nucleus, by first alkylating
a phenol and then reacting the alkylated product with an
aldehyde or ketone or functional equivalent thereof.
The introduction of R substituents onto hydroxy aromatic
compounds is usually affected by mixing an intermediate such
asan olefin homopolymer, interpolymer or a halogenat~d
analog thereof and, for example, a phenol at a tempera-
ture at about 10-200C in the presence of a suitable catalyst
such as aluminum trichloride, boron trifluoride, zinc
chloride, or the like; see, for example, U.S. Patent
3,368,972. A substituent can also be introduced by other
alkylation processes known to the art; see, for example, the
article entitled "Alkylation of Phenols" in Kirk-Othmer
"Encyclopedia of Chemical Technology", Second Edition, Vol. L,
Pages 894-895, Interscience Publishers, a division of John
Wiley & Sons, New York, 1963.
To be useful for the production of the hydroxy aromatic
compounds of this invention, the intermediate thus produced
must be a hydroxy aromatic intermediate having at least one
hydrocarbon-based substituent of at least 50 aliphatic
carbon atoms and, in addition, at least one unsubstituted
aromatic ring carbon usually located in an alpha or gamma
,i ` ','
1~75;~i5
position to an aromatic carbon bearing a hydroxyl group.
This~unsubstituted aromatic ring carbon is necessary to pro-
vide a site for the subsequent attachment of the methylol
or substituted methylol substituent. These intermediates
can be represented by the formula
(HO)xAr(H)y(R)z
wherein x, y and z are each at least one and their sum does
not exceed the available valences of Ar.
The methylol or substituted methylol group can be
introduced by reaction of the hydroxy aromatic intermediate
with a hydrocarbon-based aldehyde or functional equivalent
thereof. Suitable aldehydes include formaldehyde, benz-
aldehyde, acetaldehyde, butyraldehyde, hydroxy butyralde-
hyde, hexanals, etc. "Functional equivalents" are materials
(e.g., solutions, polvmers, hydrates, etc.) which react
as aldehydes under the conditions of the reaction and
include such materials as paraformaldehyde, hexamethylenete-
tramine, paraldehyde, formalin and methylal. Should di-
substituted methylol groups be desired, the aldehyde is
replaced with an appropriate ketone, such as acetone,
methyl ethyl ketone, acetophenone, benzophenone, and the
like. Mixtures of aldehydes and/or ketones can also be used
to produce compounds having mixtures of methylol groups.
Formaldehyde and functional equivalents are generally
preferred, since they yield the preferred methylol groups.
Introduction of the methylol groups usually takes place by
reacting the hydroxy aromatic intermediate with an
aldehyde, ketone or functional equivalent thereof in the
presence or absence of an acidic or alkaline reagent. When
the reaction takes place in the absence of such reagent,
10752~5
usually a portion of the mixture becomes acidic or alkaline
by insitu degradation of the aldehyde or ketone; excess hydroxy
aromatic intermediate can also fulfill this function.
Generally, however, the reaction of the aldehyde, ketone
or functional equivalent thereof takes place in the presence
of an alkaline reagent such as an alka]i metal or alkaline
earth metal oxide, hydroxide or lower alkoxide, at a tempera-
ture up to about 160C. Other alkaline reagents which can
be used include sodium carbonate, sodium bicarbonate,
sodium acetate, sodium propionate, pyridine, and hydrocar-
bon-based amines such as methyl amine and aniline; naturally,
mixtures of two or more bases can be used. Preferably,
the reaction takes place in the temperature range of about
30 to about 125C.; more usually, it is carried out between
70 and 100~C.
The relative proportions of hydroxy aromatic inter-
mediates, and aldehyde, ketone or functional equivalent
thereof are not critical. It is generally satisfactory to
use 0.1-5 equivalents of aldehyde and about 0.05-10.0 eguiva-
lents of alkaline reagent per equivalent of hydroxy aromaticcompound. As used herein, the term "equivalent" when
applied to a hydroxy aromatic compound indicates the weight
of such compound equal to the molecular weight thereof
divided by the number of unsubstituted aromatic carbons
bearing hydrogen atoms. As applied to the aldehyde,
ketone or functional equivalent thereof, an "equivalent"
is the weight required to produce one mole of monomeric
aldehyde. An equivalent of alkaline reagent is that weight
of reagent which when dissolved in one liter of solvent
(e.g., water) will give a one normal solution. One equiva-
lent of alkaline reagent will therefore neutralize, i.e.,
bring to pH7 a one normal solution of, for example, hydro-
chloric or sulfuric acid.
107~'~65
It is generally convenient to carry out the reaction or
the hydroxy aromatic intermediate in the presence of a
substantially inert, organic liquid diluent which may be
volatile or non-volatile. This diluent may dissolve all the
reactants, or it may not, hut in any event, it does not
substantially effect the course of the reaction under the
prevailing conditions though, in ce~tain cases, it may
promote the speed of the reaction by increasing the contact
of the reagents. Suitable diluents include hydrocarbons
such as naphtha, textile spirits, benzene, toluene, xylene;
mineral oils (which are among the preferred); synthetic oils
(as described hereinbelow); alcohols, such as isopropanol,
butanol, isobutanol, amyl alcohol, ethyl hexanols and the
like; ethers, such as triethylene or diethylene glycol mono- or
di-ethyl ether and the like, as well as mixtures of two or
more o~ these.
The reaction of the hydroxy aromatic intermediate with
aldehyde or ketone generally takes place in 0.5 to 8
hours, depending on such factors as the reaction temperature,
amount and nature of alkaline catalyst used, etc. The control
of such factors is well within the skill of the art and the
effect of these factors is apparent. After the reaction
has been completed to the desired extent, it can be substan-
tially stopped by neutralization of the reaction mixture
when an alkaline reagent is present. This neutralization
can be effected with any suitable acidic materi~l, typically
a mineral acid or an organic acid or anhydride; an acidic gas
such as carbon dioxide, hydrogen sulfide, sulfur dioxide and
the like, can also be used. Generally neutralization is
accomplished with a carboxylic acid, especially a lower
alkanoic carboxylic acid such as formic acid, acetic or
propionic acid; mixtures of two or more acids can, of
1075'~65
course, be used to accomplish the neutralization. The
neutralization is carried out at a temperature of about 30
to 150C. An amount of neutralizing a~ent sufficient to
substantially neutralize the reaction mixture is used.
Substantial neutralization means that the reaction mixture
is brought to a pH ranging between 4.5 and 8Ø Usually the
reaction mixture is brought to a minimum pH of about 6 or a
maximum pH of about 7.5.
The reaction product, i.e., the hydroxy aromatic
compositions of this invention, can be recovered from the
reaction mixture by such techniques as filtration ~for
example, to remove the product of the neutralization of the
alkaline reagent) followed by distillation, evaporation,
etc. Such techniques are well known to those skilled in the
art.
These compositions contain at least one compound which
can be represented by the general formula
~HO)xAr(H)y,(R)z(COH)g
(R') 2
wherein x, z and g are each at least one; y' is O or at least
one, the sum of x, y', z and g does not exceed the available
valences of Ar; each R' is hydrogen or a "hyd" substituent as
described above, and R is as described above. Often, however,
it is not necessary to isolate the hydroxy aromatic compound
formed from the reaction solvent, especially if it is to be
blended in a fuel or lubricant or to be used as an inter-
mediate for further reactions. In the latter case, the
reagents for further reaction (such as those discussed here-
inbelow) can be added directly to the product mixture;
alternatively, the reaction mixture can be filtered to
remove any solids present and the filtrate thus obtained
used in further reactions.
1075~65
When the reaction temperature is in the higher range,
i.e., above about 100C.,substantial amounts of ether con-
densation products can be formed. It is believed that
these condensates have the general formula
OH
HO- ~CR'2-Ar'- CR'2 ~ H
q
wherein q is a number ranging from 2 to about 10. These
condensates thus contain alkylene ether linkages, i.e.,
-CR'2O- linkages. Thus, for example, in the case of the
reaction of an alkyl phenol with formaldehyde, ether con-
densates are formed having the general formula
OH
HO- - CH2 ~ CH2O - H
_ R" q
wherein q is a number ranging from 2 to about 10 and R" is
an alkyl group of at least 50 carbon atoms. It is possible
that small amounts of such ether condensates accompany the
predominantly largely uncondensed hydroxy aromatic compounds
produced at lower temperatures.
If a strong acid, such as a mineral acid, is used for
the neutralization, it is important to control the amount
thereof present so as not to bring the reaction mixture to
a lower pH than specified hereinabove. For example, at
lower pH's, over-condensation occurs to form methylene-
bridged phenols. Such methylene-bridged phenols are not
within the scope of the present invention. The use, how-
ever, of carboxylic acids avoids this problem since they are
of sufficiently low acidity they do not promote over-con-
densation and it is not necessary to regulate so closely
the amount of carboxylic acid used.
107~ 5
The typical phenol or naphthol/formaldehyde-based
hydroxy aromatic compounds of this invention have the
general formula
OH
Ar~(cH2oH)n
R
wherein Ar' is a benzene, naphthalene, X-substituted benzene
or X-substituted naphthalene nucleus, n is 1 or 2, and R is
a hydrocarbon-based substituent of at least about 50 ali-
phatic carbon atoms, and X is selected from the group con-
sisting of lower alkyl groups, lower alkoxy groups, lower
mercapto groups, fluorine atoms, chlorine atoms and nitro
groups. An especially preferred class of hydroxy aromatic
compounds are those made from phenols and have the general
formula
OH
(HOCH2)m- ~ CH2OH
R
wherein R~ is an alkyl substituent of about 50 to about 300
carbon atoms derived from polymerization or interpolymeriza-
tion of at least one monoolefin of 2 to 10 carbon atoms, and
m is 1 or 0.
The following are specific illustrative examples of the
hydroxy aromatic compounds of the present invention and
include the best mode presently known. All parts and per-
centages in the examples and elsewhere herein are by weight
unless it is expressly stated to the contrary. All tempera-
tures are in degrees centigrade (C) unless expressly stated
to the contrary. Molecular weights are determined by vapor
phase osmometry (VPO) or gel permeation chromatography (GPC).
-13-
1075;~f~S
The textile spirits used in these examples is an aliphatic
petroleum naphtha with a boiling range of about 63-79 at
760 torr.
Example lA
Polyisobutenyl chloride (4885 parts) having a viscosity
at 99 of 1306 SUS and containing 4.7% chlorine is added to
a mixture of 1700 parts phenol, 118 parts of a sulfuric
acid-treated clay and 141 parts zinc chloride at 110-155
during a 4-hour period. The mixture is then kept at 155-
185 for 3 hours before being filtered through diatomaceous
earth. The filtrate is vacuum stripped to 165/0.5 torr.
The residue is again filtered through diatomaceous earth.
The filtrate is a su~bstituted phenol having an OH content of
1~88%.
Example lB
Sodium hydroxide (42 parts of a 20% aqueous sodium
hydroxide solution) is added to a mixture of 453 parts of
the substituted phenol described in Example lA and 450 parts
isopropanol at 30 over 0.5 hour. Textile spirits (60
parts) and 112 parts of a 37.7~ formalin solution are added
at 20 over a 0.8 hour period and the reaction mixture is
held at 4-25 for 92 hours. Additional textile spirits (50
parts), 50 parts isopropanol and acetic acid (58 parts of a
50~ aqueous acetic acid solution) are added. The pH of the
mixture is 5.5 (as determined by ASTM procedure D-974). The
mixture is dried over 20 parts magnesium sulfate and then
filtered through diatomaceous earth. The filtrate is vacuum
stripped to 25/10 torr. The residue is the desired methylol-
substituted product having an OH content of 3.29~.
Example 2A
Aluminum chloride (76 parts) is slowly added to a
-14-
1075~65
mixture o 4220 parts polyisobutenyl chloride having a
number average molecular weight, Mn, of 1000 (VPO) and
containing 4.2% chlorine, 1516 parts phenol, and 2500 parts
toluene at 60. The reaction mixture is kept at 95 under a
below~the-surface nitrogen gas purge for 1.5 hours. Hydro-
chloric acid (50 parts of a 37.5% aqueous hydrochloric acid
solution) is added at room temperature and the mixture stored
for 1.5 hours. The mixture is washed five times with a
total of 2500 parts water and then vacuum stripped to
215/1 torr. The residue is filtered at 150 through diato-
maceous earth to improve its clarity. The filtrate is a
substituted phenol having an OH content of 1.39~, a Cl
content of 0.46~ and a Mn of 898 (VPO).
Example 2B
Paraformaldehyde (38 parts) is added to a mixture of
1399 parts of the substituted phenol described in Example 2A,
200 parts toluene, 50 parts water and 2 parts of a 37.5~
aqueous hydrochloric acid solution at 50 and held for one
hour. The mixture is then vacuum stripped to 150/15 torr
and the residue is filtered through diatomaceous earth.
The f iltrate is the desired product having an O~ content
of 1.60%, Mn of 1688 (GPC) and a weight number average
molecular weight, Mw, of 2934 (GPC).
Example 3A
Boron trifluoride gas (3.8 parts) is introduced via a
sparger underneath the surface into 168 parts phenol at 49-
53 during a 0.42 hour period. A solution t519 parts)
containing 678 parts polyisobutene having an Mn of 1600
(VPO) and 133 parts benzene is added at 54-57 during a 1.7
hour period and held at 57 for 2.3 hours. A 26% aqueous
ammonia solution ~6.5 parts) is added to the reaction
iO7SZ~iS
mixture at 56-58 during a l-hour period and then the mix-
ture is kept at 69 for 0.67 hour. The mixture is filtered
through diatomaceous earth and the filtrate is vacuum
stripped to 228/15 torr~ The residue is a substituted
S phenol having an OH content of 0.91~ and a Mn of 1439 (VPO).
Example 3B
Sodium hydroxide (352 parts of~a 25~ aqueous sodium
hydroxide solution) is added to a mixture of 3740 parts of a
substituted phenol prepared as described in Example 3A, 1250
parts textile spirits and 2000 parts isopropanol at 34C.
Formaldehyde (480 parts of a 37.7~ formalin solution) is
added over a 0.75 hour period at 34. The reaction mixture
is held at 30-34 for 114 hours. Acetic acid (150 parts of
a commercially available glacial acetic acid) and 3663 parts
diluent oil is added at 30. The mixture is then vacuum
stripped to ~U~ torr. ~l~he residue is filtered through
diatomaceous earth and the filtrate is a 49~ oil solution of
the desired product having an OH content of 1.33%.
Exam~le 4
Sodium hydroxide (842 parts of a 25~ aqueous sodium
hydroxide solution) is added to a mixture of 5200 parts of a
substituted phenol, prepared as described in Example 3A
except the polyisobutene used has a Mn of 940 (VPO), 1200
parts toluene and 1200 parts isopropanol at 35. Formalde-
hyde (600 parts of a 37.7~ formalin solution) is added to
the mixture at 35 during a 0.33 hour period and the mixture
is kept at 35-30 for a 15-hour period. Additional formalde-
hyde (400 parts of a 37.7% formalin solution) is added and
the reaction mixture is held a'c 30 for a 20-hour period.
Hydrochloric acid (416 parts of a commercially available
37.5% aqueous hydrochloric acid solution) is added. The pH
-16-
1075;~j5
of the mixture is 6. Ben~ene (2000 parts) and 1500 parts
additional toluenc are added and the mixture is azeotroped
to 95 under a partial vacuum. Diluent oil (2000 parts) is
added and the mixture is then vacuum stripped to 95/30 torr.
The residue is filtered through diatomaceous earth and the
filtrate is a 30~ oil solution of the desired product having
an OH content of 1.69%.
Example 5
Benzene (200 parts) is added to 1110 parts of the
azeotroped to 95 under a partial vacuum mixture as described
in Example 4 and the reaction temperature is raised to 160
and kept there for 3 hours. The mixture is then filtered
through diatomaceous earth at 150 and the filtrate is
vacuum stripped to 150/10 torr. The residue is the desired
product having an OH content of 1.73% and a Mn of 5252 (GPC)
and a Mw of 2171 (G~C3.
Example 6
Sodium hydroxide t8 parts of a 50~ aqueous sodium
hydroxide solution) and 145 parts paraformaldehyde are added
to a mixture of 2240 parts of a substituted phenol prepared
as described in Example 2A except the polyisobutene used has
a Mn of 940 (VPO), and 1271 parts diluent oil at 60 and the
mixture kept at 80 for 22 hours. Acetic acid (6 parts of
glacial acetic acid) is added and the mixture is held at
150 for 2 hours and then filtered through diatomaceous
earth. The filtrate is a 35% oil solution of the desired
product having an OH content of 1.10%.
Example 7
.
Sodium hydroxide (32 parts of a 50% aqueous sodium
hydroxide solution) and 290 parts paraformaldehyde are added
to a mixture of 4480 parts of the substituted phenol used in
lO~S'~S
Example 6 and 3099 parts diluent oil at 40-50; the mixture
is kept at 80-85 for a 14-hour period. ~cetic acid (36
parts of glacial acetic acid) is added at 60. The mixture
is held at 110-130 for a period of 12 hours and then is
filtered through diatomaceous earth. The filtrate is a 40~
oil solution of the desired product having an OH content of
1.05%.
Example 8
Sodium hydroxide (8 parts of a 50% aqueous sodium
hydroxide solution) and 145 parts paraformaldehyde are added
to a mixture of 2080 parts of the substituted phenol de-
scribed in Example 4 and 1400 parts diluent oil at 55 and
the mixture is held at 70-78 for a 7-hour period. Acetic
acid (9 parts glacial acetic acid) is added at 60 and then
i5 the r.ixture is he~d at 13~ f~r a ~-hour p2riod. The resi-
due is a 40~ oil solution of the desired product having an
OH content of 1.28% and a viscosity at 99 of 884 SUS.
The compositions of this invention are useful in and of
themselves as anti-rust and anti-corrosion agents for fuels
and lubricants. They are also useful as intermediates for
the production of compositions that function in fuels and
lubricants as detergents and dispersants for sludge formed
in internal combustion engines.
The compositions of this invention 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, such as automobile and truck
-18-
1075;~S
engines, two-cycle engines, marine and railroad diesel
engines, and the like. They can also be used in gas en-
gines, stationary power engines, turbines and the like.
Automatic transmission fluids, transaxle lubricants, gear
lubricants, metal-working lubricants, hydraulic fluids and
other lubricating oil and grease compositions can also
benefit from the incorporation therein of the compositions
of the present invention.
Natural oils include animal oils and vegetable oils
(e.g., 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 olls. Synthetic lubricatiilg Gils include
hydrocarbon oils and halosubstituted hydrocarbon oils such
as polymerized and interpolymerized olefins (e.g., poly-
butylenes, polypropylenes, propylene-isobutylene copolymers,
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,
etc.); alkylated diphenyl ethers and alkylated diphenyl
sulfides and the derivatives, analogs and homologs thereof
and the like.
Alkylene oxide polymers and interpolymers and deri-
vatives thereof where the terminal hydroxyl groups have been
modified by esterification, etherification, etc. constitute
another class of known synthetic lubricating oils. These
107S2~5
are exemplified by the oils prepared throu~h polymerization
of ethylene oxide or propylene oxide, 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
mono- and polycarboxylic esters thereof, for example, the
acetic acid esters, mixed C3-C 8 fatty acid esters, or the
0 Cl 30Xo acid diester of tetraethylene glycol.
Another 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, 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.
Esters useful as synthetic oils also include those made
from Cs to C~ 2 monocarboxylic acids and polyols and polyol
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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 of 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)siloxanes,
etc.). Other synthetic lubricating oils include liquid
esters of phosphorus-containing acids (e.g., tricresyl
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
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
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iO75;~:iS
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 breakdown products.
In general, about 0.05-20.0, preferably 0.1-10 parts
(by weight) of a composition of this invention is dissolved
or stably dispersed in 100 parts of oil to produce a satis-
factory lubricant. The invention also contemplates the use
of other additives in combination with the composition of
this invention. Such additives include, for example, auxi-
liary detergents and dispersants of the ash-producing or
ashless type, oxidation inhibiting agents, pour point
depressing agents, extreme pressure agents, color stabilizers
and anti-foam agents.
The fuel compositions of the present invention contain
a major proportion of a normally liquid fuel, usually a
hydrocarbonaceous 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 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 contemplated.
Examples of such mixtures are combinations of gasoline and
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107S2~;S
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 60~C. at the
10% distillation point to about 205C. at the 90~ distilla-
tion point.
Generally, these fuel composit~ons contain an amount of
the compound of this invention sufficient to impart
anti-oxidant and/or dispersant and detergent properties to
the fuel; usually this amount is about 1 to about 10,000,
preferably 4 to 1,000, parts by weight of the reaction
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 ethylene dibromide), deposit pre-
ventors or modifiers such as triaryl phosphates, dyes,
cetane improvers, anti-oxidants such as 2,6-di-tertiary-
butyl-4-methylphenol, rust inhibitors, such as alkylated
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 inven-
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1~75;~S
tion are combined with other ashless dispersants in gaso-
line. Such ashless dispersants are prefereably esters of a
mono- or polyol and a high 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, British Patents 981,850 and 1,055,337 and
U.S. Patents 3,255,108; 3,311,558; 3,331,776; 3,346,354;
3,522,179; 3,579,450; 3,542,680; 3,381,022; 3,639,242;
3,697,428;3,708,522; and British Patent Specification
1,306,529. 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
compositions are combined with Mannich condensation products
formed from substituted phenols, aldehydes, polyamines, and
amino pyridines to make lubricants and/or fuel additives.
Such condensation products are described in U.S. Patents
3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277.
The compositions 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
liquid organic solvent/diluent such as mineral oil, xylene,
or a normally liquid fuel as described above, to form an
additive concentrate which is then added to the fuel or
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1075'~S
lubricating oil in sufficient amounts to form the inventive
fuel and lubricant composition described herein. These
concentrates generally contain about 20 to about 90 percent
of the composition of this invention and can contain in
addition any of the above-described conventional additives,
particularly the afore-aescribed ashless dispersants in the
aforesaid proportions. The remainder of the ~oncentrate is
the solvent/diluent.
As well as serving as additives in and of themselves,
the compounds of this invention can be used as inter-
mediates to form compositions which are also useful as
additives in the afore-described fuels and lubricants.
For example, the methylol-substituted phenols of this
invention can be condensed with amines-and polyamines having
at least one~ NH group to form useful engine sludge dis-
persan~/detergent compositions. -Such condensation can be
conveniently carried out by heating the phenol/amine mixture
in the presence of benzene or toluene while removing the
by-product water by azeotropic distillation. Further details
of such condensations can be found in French Patent 75 07709,
filed March 12, 1975.
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