Note: Descriptions are shown in the official language in which they were submitted.
1055051
This invention relates to a new chemical process, and
to compositions prepared by that process which are useful in
lubricants and fuels. More particularly, it relates to a
method for preparing an oil-soluble nitrogen-containing
S composition of matter which comprises:
(1) reacting at least one hydroxyaromatic compound con-
taining an aliphatic or alicyclic substituent of at least
about 6 carbon atoms with at least one aldehyde or precursor
thereof in the presence of an alkaline reagent, at a tempera-
ture up to about 125C.; then
(2) substantially neutralizing the intermediate thus
formed at a temperature up to abou~ 150C.; and then
(3) reacting the neutralized intermediate with at least
one amino compound which contains one or more amino groups
having at least one hydrogen atom directly bonded to amino
nitrogen.
The J~annich reaction between active hydrogen compounds,
formaldehyde and compounds containing amino groups has been
known for some time. It is also known (e.g., from U.S.
Patents 3,368,972 and 3,649,229) that Mannich bases derived
from certain alkylphenols function as dispersants in lubri-
cants and fuels. The preparation of such Mannich bases is
described in U.S. Patent 3,737,465.
In view of the increasingly severe conditions under
which internal combustion engines are operated, it is of
continuing interest to prepare more effective dispersant
additives. Due to financial considerations, raw material
supplies, and other factors, it is also desirable to develop
alternate dispersants and methods for their preparation.
.
-- 1 --
lOS50Sl
A principal object of the present invention, therefore,
is to provide a new method for producing lubricant and fuel
additives.
A further object is to provide an improved method for
producing compositions useful in lubricants and fuels.
Still another object is to provide improved additives
for use in lubricants and fuels, concentrates containing these
additives, and improved lubricant and fuel compositions
containing said additives.
These and other ob~ects can be achieved according to
the description of the invention provided hereafter.
According to this invention, an oil-soluble nitrogen-
containing compositions, useful as additives in lubricants
and fuels, are prepared from three reagents by means of a
specific reaction sequence discussed herein.
The first reagent is a hydroxyaromatic compound. This
torm includes phenols (which are preferred); carbon-, oxygen-,
sulfur- and nitrogen-bridged phenols and the like as well as
phenols directly linked through covalent bonds (e.g.g 4,4'-bis
(hydroxy) biphenyl); hydroxy compounds derived from fused-ring
hydrocarbon (e.g., naph~hols and the like); and dihydroxy
compounds such as catechol, resorcinol and hydroquinone.
Mixtures of one or more hydroxyaromatic compounds can be used
as the first reagent.
The hydroxyaromatic compounds used in the method of
this invention are those substituted with at least one, and
preferably not more than two, aliphatic or alicyclic sub-
stituents, R', having at least about 6 (usually at least about 30,
more preferably at least about 50) carbon atoms and up to
about 7000 carbon atoms. Examples of such substituents
- ~ - 2 -
105SOSl
derived from the polymerization of olefins such as ethylene,
propylene, l-butene, 2--butene, isobutene and the like. Both
homopolymers (made from a single olefin monomer) and inter-
polymers (made from two or more of olefin monomers) can
serve as sources of these substituents and are encompassed
in the term "polymers" as used herein and in the appended
claims. Substituents derived from polymers of ethylene,
propylene, l-butene and isobutene are preferred, especially
those containing at least about 30 and preferably at least
about 50 aliphatic carbon atoms. In some instances, however,
higher molecular weight substituents, e.g., those having
molecular weights of about 50,000-100,000, are desirable
since such substituents can impart viscosity index improvîng
properties to the composition. Such higher molecular weights
can be calculated from the inherent or intrinsic viscosity
using the Mark-Houwink equation and are called viscosity
average molecular weights (Mv). Number average molecular
weights (Mn) ranging from about 420 to 10,000 are conven-
iently measured by vapor pressure osmometry (VPO). (And
this method is used for the Mn ranges set forth herein.)
The aliphatic and alicyclic substituents as well as the
aryl nuclei of the hydroxyaromatic compound are generally
described as "hydrocarbon-based" substituents.
As used herein, the term "hydrocarbon-based substi-
tuent" denotes a substituent having a carbon atom directly
attached to the remainder of the molecule and having pre-
dominantly hydrocarbyl character within the context of this
invention. Such substituents include the following:
(1) Hydrocarbo.. substituents, that is aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cyclo-
lOSS105~
alkenyl) substituents, aromatic, aliphatic- and alicyclic-
substituted aromatic nuclei and the like, as well as cyclic
substituents wherein a ring is completed through another
portion of the molecule (that is, any two indicated substi-
tuents may together form an alicyclic radical).
(2) Substituted hydrocarbon substituents, that is,those containing non-hydrocarbon radicals which, in the
context of this invention, do not alter the predominantly
hydrocarbyl character of the substituent. Those skilled in
the art will be aware of suitable radicals (e.g., hydroxy,
halo, (especially chloro and fluoro), alkoxyl, mercapto,
alkyl mercapto, nitro, nitroso, sulfoxy, etc., radicals).
(3) Hetero substituents, that is, subsitutents which,
while predominantly hydrocarbon in character within the
context of this invention, contain atoms other than carbon
present in a chain or ring otherwise composed of carbon
atoms. Suitable hetero atoms will be apparent to those
skilled in the art and include, for example, sulfur, oxygen
and nitrogen and form substituents such as, e.g., pyridyl,
furanyl, thiophenyl, imidazolyl, etc.
In general, no more than about three radicals or hetero
atoms, and preferably no more than one, will be present for
each 5 carbon atoms in the hydrocarbon-based substituent.
Preferably, there will be no more than three radicals per 10
carbon atoms.
Preferably, the hydrocarbon-based substituent in the
compositions of this invention are free from acetylenic
unsaturation. Ethylenic unsaturation, when present, pre-
ferably will be such that no more than one ethy;enic linkage
10~/505~
will be present for every 10 carbon~to-carbon bonds in the
substituent. The substituents are usually preferably hydro-
carbon in nature and more preferably, substantially saturated
hydrocarbon. ~s used in this specification and the appended
claims, the word "lower" denotes substitutents, etc. con-
taining up to seven carbon atoms; for example, lower alkoxy,
lower alkyl, lower alkenyl, lower aliphatic aldehyde.
~ ntroduction of the aliphatic or alicyclic substituent
onto the phenol or other hydroxyaromatic compound is usually
effected by mixing a hydrocarbon (or a halogenated derivative
thereof, or the like) and the phenol at a temperature of
about 50-200C. in the presence of a suitable catalyst, such
as aluminum trichloride, boron trifluoride, zinc chloride or
the like. Reference may be made to, for example, U.S. Patent
3,368,972 for further disclosures in this regard. The
substituent can also be introduced by other alkylation
processes known in the art.
The mono- or di-hydroxy aromatic compounds that are used
as the first reagent can be represented by the general formula
(IH)l-2
Ar
wherein Ar is an aromatic moiety having at least one aliphatic
or alicyclic substituent R' as hereinabove referred to.
Especially preferred as the first reagent are mono-
substituted phenols of the general formula
OH
~ R'
wherein R' is an aliphatic or alicyclic hydrocarbon-based
substituent of Mn (V.P.O.) of about 420 to about 10000.
~' ~
~.
l(~SS~)Sl
The said Mn value of about 10,000 corresponds to a oontent
of up to about 700 carbon atoms.
The second reagent is a hydrocarbon-bas~d carbonyl
oompound, preferably a lower aliphatic aldehyde. Suitable
aldehydes include formaldehyde, benzaldehyde, acetaldehyde, the
butyraldehydes, hydroxybutyraldehydes and heptanals, as well
as aldehyde precursors which react as aldehydes under the
1055051
conditions of the reaction such as para~ormaldehyde, hexa-
methylene tetraamine, paraldehyde, formalin and methal.
Formaldehyde and its polymers (e.g~, paraformaldehyde trioxane)
are preferred. Mixtures of carbonyl compounds may be used as
the second reagent.
The third reagent is a compound containing an amino
group having at least one hydrogen atom directly bonded to amino
nitrogen. Suitable amino compounds are those containing only
primary, only secondary, or both primary and secondary amino
groups, as well as polyamines in which all but one of the amino
groups may be tertiary. Suitable amino compounds include ammonia,
aliphatic amines, aromatic amines, heterocyclic amines and carbo-
cyclic amines, as well as polyamines such as alkylene amines,
arylene amines, cyclic polyamines and the hydroxy-substituted
derivatives of such polyamines. Mixtures of one or more amino
compounds can be used as the third reagent.
Specific amines of these types are methylamine, N-
methylethylamine, ~-methyl-octylamine, ~-cyclohexyl-aniline,
dibutylamine, cyclohexylamine, aniline, di(p-methyl-phenyl)-
amine, ortho, meta and para-aminophenol, dodecylamine,
octadecylamine, o-phenylene-diamine, N,N'-di-n-butyl-p-
phenylenediamine, morpholine, N,N-di-n-butyl-p-phenylene-
diamine, piperazine, tetrahydropyrazine, indole, hexahydro-
1,3,5-triazine, 1-H-1,2,4-triazole, bis-(p-aminophenyl)-
methane, methanediamine, cyclohexamine, pyrrolidine, 3-
amino-5, 6-diphenyl-1,2,4-triazine, quinonediimine, 1,3-
indandiimine, 2-octadecyl-imidazoline, 2-phenyl-4-methyl-
imidazolidine, oxazolidine, ethanolamine, diethanolamine, N-
3-aminopropyl morpholine, phenothiazine, 2-heptyl-oxazolidine,
2-heptyl-3-(2-aminopropyl) imidazoline, 4-methyl-imidazoline,
105SOSl
1,3-bis(2-aminoethyl)imidazoline, 2-heptadecyl-4 (2-hydroxy-
ethyl)imidazoline and pyrimidine.
A preferred group of amino compounds consists of poly-
amines, especially alkylene polyamines conforming for the
most part to the formula
H-N-(-alkylene-~-)-nH
A A
wherein n is an integer preferably less than about 10, A is
a hydrocarbon-based substituent or hydrogen atom, and the
alkylene radical is preferably a lower alkylene radical of
up to 7 carbon atoms. Mixtures of such polyamines are
similarly useful. The alkylene polyamines include principally
polymethylene: amines, ethylene amines, butylene amines,
propylene amines, trimethylene amines, pentylene amine-s,
- hexylene amines, heptylene amines, octylene amines, other
polymethylene amines, and also the cyclic and the higher
homologs of such amines such as piperazines and aminoalkyl-
substituted piperazines. They are exemplified specifically
by: ethylene diamine, triethylene tetramine, propylene
diamine, decamethylene diamine, octamethylene diamine,
di(heptamethylene)triamine, tripropylene tetramine, tetra-
ethylene pentamine, trimethylene diamine, pentaethylene
hexamine, di~trimethylene)triamine, l-(2-aminopropyl)piper-
azine, 1,4-bis(2-aminoethyl)piperazine, and 2-methyl-1-(2-
aminobutyl)piperazine. Higher homologs such as are obtained
by condensing two or more of the above illustrated alkylene
amines likewise are useful.
The ethylene polyamines are especially useful. They
are described in sol.,_ ~etail under the heading "Diamines and
Higher Amines" in "Encyclopedia of Chemical Technology",
Second Edition, Kirk and Othmer, Volume 7, pages 27-39,
lOS150S~
Interscience Publishers, New York (1965~. Such compounds
are prepared most conveniently by the reaction of an alkylene
chloride with ammonia. The reaction results in the pro-
duction of somewhat complex mixtures of alkylene polyamines,
including cyclic condensation products such as piperazines.
These mixtures find use in the process of this invention.
On the other hand, quite satisfactory products may be
obtained also by the use of pure alkylene polyamines. An
especially useful alkylene polyamine for reasons of economy
as well as effectiveness of the products derived therefrom
is a mixture of ethylene amines prepared by the reaction of
ethylene chloride and ammonia and containing about 3-7 amino
groups per molecule.
Hydroxyalkyl-substituted alkylene polyamines, i.e.,
alkylene polyamines ha~ing one or more hydroxyalkyl substi-
tuents on the nitrogen atoms, likewise are contemplated for
use herein. The hydroxyalkyl-substituted alkylene poly-
amines are preferably those in which the alkyl group is a
lower alkyl group, i.e., an alkyl having less than 8 carbon
atoms. Examples of such amines include N-(2-hydroxyethyl)-
ethylene diamine, N,N'-bis(2-hydroxyethyl)ethylene diamine,
1-(2-hydroxyethyl)piperazine, mono-hydroxypropyl-substituted
diethylene triamine, 1,4-bis(2-hydroxypropyl)piperazine, di-
hydroxypropyl-substituted tetraethylene pentamine, N-(3-
hydroxypropyl)tetramethylene diamine, etc.
Higher homologs such as are obtained by condensation of
the abo~e-illustrated alkylene polyamines or hydroxyalkyl-
- substituted alkylene polyamines through amino radicals or
through hydroxy radicals are likewise useful. Tt will be
lOS5051
appreciated that condensation through amino radicals results
in a higher amine accompanied with removal of ammonia and
that condensation through the hydroxy radicals results in
products containing ether linkages accompanied with removal
of water.
Another preferred class of amino'compounds are aromatic
amines containing about 6 to about 30 carbon atoms and at
least one primary or secondary amino groups. Examples
include aryl amines such as the isomeric amino phenols,
aniline, N-lower alkyl anilines, heterocyclic amines such as
the isomeric amino pyridines, the isomeric naphthyl amines,
phenothiazine, and their Cl-3 o hydrocarbyl substituted
analogs such as N-phenyl-alpha-naphthyl amine. Aromatic
diamines such as the phenylene and naphthylene diamines can
also be used.
Other suitable amino compounds include ureas, thioureas,
hydroxylamines, hydrazines, guanidines, amidines, amides,
thioamides, cyanamides, amino acids and the like. Specific
examples illustrating such compounds are: hydrazine,
phenylhydrazine, N,N'-diphenylhydrazine, octadecylhydrazine,
benzoylhydrazine, urear thiourea, N-butylurea, stearylamide,
oleylamide, guanidine, l-phenylguanidine, benzamidine,
octadecamidine, N,N'-dimethylstearamidine, cyanamide,
dicyandiamide, guanylurea, aminoguanidine, iminodiacetic
acid, iminodipropionitrile, etc.
In the first step of the method of this invention, the
hydroxyaromatic compound is reacted with the aldehyde in the
presence of an alkaline reagent, at a temperature up to
about 125C. and pre erably about 50-125C.
~SSOSl
The alkaline reagent is typically a strong inorganic
base such as an alkali metal based (e.g., sodium or potas-
sium hydroxide). Other inorganic and organic bases can be
used as the alkaline base such as Na2CO3, NaH~O3, sodium
acetate, pyridine, and hydrocarbon-based amines such as
methylamine, aniline, and alkylene polyamines, etc.) may
also be used. Mixtures of one or more alkaline bases may be
used.
The relative proportions of the various reagents
employed in the first step are not critical; it is generally
satisfactory to use about 1-4 equivalents of aldehyde and
about 0.05-10.0 equivalents of alkaline reagent per equiva-
lent of hydroxyaromatic compound. (As used herein, the term
"equivalent" when applied to a hydroxyaromatic compound
indicates a weight equal to the molecular weight thereof
divided by the number of aromatic hydroxyl groups directly
bonded to an aromatic ring per molecule. As applied to the
aldehyde or precursors thereof, an "equivalent" is the
weight required to produce one more molecule of monomeric
aldehyde. An equivalent of alkaline reagent is that weight
of reagent that when dissolved in one liter of solvent will
give a normal solution. One equivalent of alkaline reagent
will neutralize (i.e., bring to pH 7.0) a 1.0 normal solu-
tion of, e.g., hydrochloric or sulfuric acid.)
It is generally convenient to carry out the first step
in the presence o~ a substantially inert, organic liquid
diluent, which may be volatile or non-volatile. A substan-
tially inert, organic liquid diluent which may or may not
dissolve all the reactants, is a material which does not
substantially react with the reagents under the reaction
conditions. Suitable diluents include hydrocarbons such as
naphtha, textile spirits, mineral oil (which is preferred),
10,550Sl
synthetic oils (as described hereinbelow), benzene, toluene
and xylene; alcohols such as isopropanol, n-butanol, iso-
butanol and 2-ethylhexanol; ethers such as ethylene or
diethylene glycol mQno- or diethyl ether; or the like, as well
as mixtures thereof.
The intermediates that are obtained in the first step,
which comprises reaction of a substituted mono- or di-hydroxy
aromatic compounds with an aldehyde, can be represented generally
by the following formNla:
(iH)1-2
Ar(CRH0~) and/or
(IH)1 2
H0 ~ CRH Ar CRH0 ~ H
wherein each R is independently hydrogen or a lower hydro-
carbon-based group, Ar is an aromatic mDiety having at least
one aliphatic or alicyclic hydrocarbon-based substituent,
R', having at least 6 carbon atoms; and x is an integer of
abcut 1 to about 10.
The second step is the substantial neutralization of
the intermediate obtained in the first st~p. Neutralization
may be effected with any suitable acidic material, typically
a mineral acid or an organic acid or anhydride. Acidic
gases such as carbon dioxide, hydrogen sulfide, and sulfur
dioxide may also be used. Preferably neutralization is
accomplished with carboxylic acids, especially lower hydro-
carbon-based carboxylic acid such as formic, acetic or
butyric acid. Mixtures of one or more acidic materials can
be used to acoomplish neutralization. The temperature of
,~ - 11 -
''~s
. .
lOSSOS~
neutralization is up to about 150C., preferably about 50-
150C. Substantial neutralization means the reaction
mixture is brought to a pH ranging be~ween about 4.5 and
8.o. Preferably, the reaction mixture is brought to a
minimum pH of about 6 or a maximum of about 7.50
The neutralized intermediate is a mixture comprising
hydroxyalkyl derivatives of the hydroxyaromatic compound and
ether condensation products thereof. Thus, when the inter~
mediate is made from a mono-substituted phenol, the inter-
mediate typically is a mixture of compounds of the generalformulae
OH OH
~/or _ CH20-- 11
- lla -
lO~iSOS~
wherein R' is the hereinbefore-described aliphatic or alicyclic
hydrocarbon-based substituent of about 6 to about 7000 carbon
atoms and x is an integer of about 1 to 10. Preferably R' has
an Mn (V.PØ) of about 420 to about 10,000. If a strong acid
such as a mineral acid is used for neutralization, it is
important to regulate the amount thereof present so as not to
bring the reaction mixture to a lower pH than that specified
hereinabove, in order to avoid overcondensation to form
methylene-bridged phenols rather than an intermediate
containing ether oxygens. However, carboxylic acids such as
acetic acid do not readily promote overcondensation and it is
therefore unnecessary to regulate so closely the amount of
carboxylic acid used.
In the third step, the neutralized intermediate is
reacted with the amino compound, typically at a temperature
between about 25-C. and about 225C. and usually about 55-
180C. The ratio of reactants in the third step is not
critical but about 1-6 equivalents of amine reactant are
generally employed per equivalent of the neutralized inter-
mediate. (The equivalent weight of the amine is the mole-
cular weight thereof divided by the number of hydrogens bonded
to nitrogen atoms present per molecule and the equivalent
weight of the neutralized intermediate is its molecular weight
divided by the number of -CRH0- units present derived from the
aldehyde. The number of equivalents of the intermediate is
conventionally calculated by dividing the moles of intermediate
by the moles of aldehyde used to make it.) It is frequently
convenient to use a substantially inert liquid diluent,
typically the same one used in the first step.
- 12 -
i_~
~OSS~)5~
The course of the reaction betwePn the neutralized
intermediate and the amine may be determined by measuxing
the amount of water removed by distillation, azeotropic
distillation or the like. When water evolution has ceased,
the reaction may be considered complete and any solids
present may be removed from the mixture by conventional means;
e.g., filtration, centrifugation, or the like, affording the
desired product. It is ordinarily unnecessary to otherwise
isolate the product from the reaction mixture or purify it.
The method of this invention is illustrated by the
following examples. A11 parts are by weight and all molecular
weights are determined by V.PØ unless otherwise indicated.
ExamPle 1
A mixture of 1560 parts (1.5 equivalents) of a
polyisobutylphenol having a molecular weight of about 885, 1179
parts of mineral oil and 99 parts of n-butyl alcohol is heated
to 80C. under nitrogenJ with stirring, and 12 parts
(0.15 equivalent) of 50% aqueous sodium hydroxide solution is
added. The mixture is stirred for 10 minutes and 99 parts
(3 equivalents) of paraformaldehyde is added. The mixture is
stirred at 80-88C. for 1.75 hours and is then neutralized by
the addition of 9 parts (0.15 equivalent) of acetic acid.
To the solution of the intermediate thus obtained is
added at 88C., with stirring, 172 parts (4.2 equivalents) of a
commercial polyethylene polyamine mixture containing about 3-7
nitrogen atoms per molecule and about 34.5% by weight nitrogen.
The mixture is heated over about 2 hours to 150C. and stirred
at 150-160-C. for three hours, with volatile material beirg
removed by distillation. The remainder of the volatiles are
- 13 -
B~
lOtiSOSl
then stripped at 160C./30 torr, and the residue is filtered
at 150C., using a commercial filter aid material, to yield
the desired product as a filtrate in the form of 60
solution in mineral oil containing 1.95~ nitrogen.
ExamPle 2
A solution of 4576 parts (1~ 4 equivalents) of the
polyisobutylphenol of Example 1 in 3226 parts of mineral oil
is heated to 55C. under nitxogen, with stirring, and 18
parts (0.22 equivalent) of 50~ aqueous sodium hydroxide
solution is added. The mixture is stirred for 10 minutes and
then 320 parts (9.68 e~uivalents) of paraformaldehyde is
added. The mixture is heated at 70-80C. for 13 hours, and
is then cooled to 60C. whereupon 20 parts (0.33 equivalent)
of acetic acid is added. The mixture is then heated at 110C.
for 6 hours while being blown with nitrogen to remove volatile
materials. Nitrogen blowing is continued at 130C. for an
additional 6 hours, after which the solution is filtered at
120C., using a filter aid material.
To the solution of an intermediate (i.e. alkylphenol-
formaldehyde condensate), that i5 obtained at 65C., is added184 parts (4.48 equivalents) of the polyethylene polyamine of
Example 1. The mixture is heated at 110-135C. over 4 hours
and is then blown with nitrogen at 150-160C. for 5 hours as
volatiles are removed. Mineral oil, 104 parts, is added and
the mixture is filtered at 150C., using a filter aid material,
to yield the desired product as a 60% solution in mineral oil
containing 1.80~ nitrogen.
Example 3
To 366 parts (0.2 equivalent) of the intermediate
- 14 -
~05iSOSl
solution of alkylphenol-formaldehyde condensate of Example 2
is added at 60C., with stirring, 43.4 parts (0.3 equivalent)
of N-(3-aminopropyl)-morpholine. The mixture is heated at
110-130C., with. _ _ _
/
- 14a -
,... ~, ~
lOti50S~
nitrogen blowing, for 5 hours. It is then stripped of
volatiles at 170C./16 torr, and filtered using a filter aid
material. The filtrate is the desired product (62.6% solution
in mineral oil) containing 1.41% nitrogen.
Example 4
Following the procedure of Example 3, a reaction pro-
duct is prepared from 366 parts (0.2 equivalent) of the
alkylphenol-formaldehyde condensate of Example 2 and 31.5
parts (0.3 equivalent) of diethanolamine. It is obtained as
a 62.9% solution in mineral oil, containing 0.70% nitrogen.
Example 5
. .
A mixture of 2600 parts (2.5 equivalents) of the poly-
sobutylphenpl of Example 2, 750 parts of textile spirits
~ and 20 parts (0.25 equivalent) of 50~ aqueous sodium hydroxide
is heated to 55C. under nitrogen, with stirring, and 206
parts (6.25 equivalents) of paraformaldehyde is added.
Heating at 50-55C., with stirring, is continued for 21
hours after which the solution is blown with nitrogen and
heated to 85C. as volatile materials are removed. Acetic
acid, 22 parts (0.37 equivalent), is added over one-half
hour at 85-90C., followed by 693 parts of mineral oil.
To 315 parts (0.231 equivalent) of the alkylphenol-
formaldehyde intermediate prepared as described above is
added under nitrogen, at 65C., 26.5 parts (0.647 equivalent)
of the polyethylene polyamine mixture of Example 1. The
mixture is heated at 65-gOC. for about 1 hour, and is then
heated to 120-130C. with nitrogen blowing, and finally to
145-155C. with continued nitrogen blowing for 3-1/2 hours.
Mineral oil, 57 parts, is added and the solut;~n is filtered
at 120C., using a filter aid material. The filtrate is
l(;)~OS~
the desired product (69.3% solution in mineral oil)
containing 2.11~ nitrogen.
ExamPle 6
A solution of 340 parts (0.25 equivalent) of the
alkylphenol-formaldehyde intermediate solution of Example 5
in 128 parts of mineral oil is heated to 45C. and 30 parts
(0.25 equivalent) of tris-(methylol)methylamine is added, with
stirring. The mixture is heated to 90C. over 1/2 hour, and
is then blown with nitrogen at 90-130C. for 3 hours, with
stirring. Finally, it is heated to 150-160C. for 5 hours,
with nitrogen blowing, cooled to 125C. and filtered, using a
filter aid material. The filtrate is the desired product
(60% solution in mineral oil) containing 0.19% nitrogen.
ExamPle 7
To a mixture of 1560 parts (1.5 equivalents) of the
polyisobutylphenol of Example 2 and 12 parts (0.15 equivalent)
of 50% aqueous sodium hydroxide solution is added at 68C.,
with stirring, 99 parts (3 equivalents) of paraformaldehyde.
The addition period is 15 minutes. The mixture is then heated
to 88C. and 100 parts of a mixture of isobutyl and primary amyl
alcohols is added. Heating at 85-88C. is continued for 2 hours
and then 16 parts of glacial acetic acid is added and the
mixture is stirred for 15 minutes and vacuum stripped at 150C.
To the residue is added 535 parts of mineral oil, and the oil
solution is filtered to yield the desired intermediate.
To 220 parts (0.15 equivalent) of the intermediate
prepared as described above is added 7.5 parts (0.15 equivalent)
of hydrazine hydrate. The mixture is heated to 80-105C. and
stirred at that temperature for 4 hours. Acetic acid, 0.9 part,
- 16 -
lOSSOS~
is then added and stirring is continued at 95-125C. for an
additional 6 hours. A further 7.5-part portion of hydrazine
hydrate is added and heating and stirring are continued for
8 hours, after which the product is stripped of volatiles
under vacuum at 124C. and 115 parts of mineral oil is added.
Upon filtration, the desired product (50% solution in mineral
oil) is obtained; it contains 1.19~ nitrogen.
Example 8
A mixture of 6240 parts (6 equivalents) of the poly-
isobutylphenol of Example 2 and 2814 parts of mineral oil
is heated to 60C. and 40 parts (0.5 equivalent) of 50~ aqueous
sodium hydroxide solution is added, with stirring. The mixture
is stirred for 1/2 hour at 60C., and 435 parts (13.2 equiva-
lents) of 91% aqueous formaldehyde solution is added at
75-77C. over 1 hour. Stirring at this temperature is continued
for 10 hours, after which the mixture is neutralized with 30
parts of acetic acid and stripped of volatile materials. The
residue is filtered, using a filter aid material.
A mixture of 629 parts (0.4 equivalent) of the
resulting intermediate solution and 34 parts (0.4 equivalent) of
dicyandiamide is heated to 210C. under nitrogen, with stirring,
and maintained at 210-215C. for 4 hours. It is then filtered
through a filter aid material and the filtrate is the desired
product (71~ solution in mineral oil) containing 1.04~ nitrogen.
Example 9
A mixture of 1792 parts (1.6 equivalents) of the poly-
isobutylphenol of Example 2 and 1350 parts of xylene is heated to
60C. and 12.8 parts (0.16 equivalent) of 50~ aqueous sodium
hydroxide solution is added, with stirring. The mixture is
- 17 -
10,5S0 5~
stirred at 60-65c. for 10 minutes, and then 108 parts
(3.28 equivalents) of paraformaldehyde is added. Heating
is continued at 65-75c~ for 5 hours, after which 14.3 parts
(0.24 equivalent) of acetic acid is added. The acidified
mixture is heated at 75-125C. for l/2 hour and then stripped
under vacuum. The resulting intermediate solution is
filtered through a filter aid material.
To 2734 parts (1.4 equivalents) of the above-
described intermediate solution, maintained at 65c., is added
lo 160.7 parts (3.92 equivalents) of the polyethylene polyamine
of Example 1. The mixture is heated for l-l/2 hours at
65-110c. and for l-l/2 hours at 110-140C., after which heating
at 140C. is continued with nitrogen blowing for 11 hours, while
a xylene-water azeotrope is collected by distillation. The
residual liquid is filtered at 100C., using a filter aid
material, and the filtrate is the desired product (60%
solution in xylene) containing 1.79% nitrogen.
Example 10
A mixture of 3740 parts (2 equivalents) of a poly-
isobutylphenol in which the polyisobutene substituent has a
molecular weight of about 1600, 1250 parts of textile spirits
and 2000 parts of isopropyl alcohol is stirred and 352 parts
(2.2 equivalents) of 50% aqueous sodium hydroxide solution is
added, followed by 480 parts (6 equivalents) of 38~ aqueous
formaldehyde solution. The mixture is stirred for 2 hours,
allowed to stand for 2 days and then stirred again for 17 hours.
Acetic acid, 150 parts (2.5 equivalents) is added and the mixt-
ure is stripped of volatile materials under vacuum. The
remaining water is removed by adding benzene and a æotropically
- - 18 -
1055051
distilling; during the distillation, 1000 parts of mineral
oil is added in 2 portions. The residue is filtered through
a filter aid material to yield the desired intermediate.
To 430 parts (0.115 equivalent) of the intermediate
solution, at 90C., is added with stirring 14.1 parts
(0.345 equivalent) of the polyethylene polyamine of Example 1.
The mixture is heated at 90-120C. for 2 hours and then at
150-160C. for 4 hours, with nitrogen blowing. After all
volatile materials have been removed, the resulting solution
is filtered to yield the desired product (52~ solution in
mineral oil) which contains 1.03% nitrogen.
Example 11
A solution of 6650 parts (25 equivalents) of tetra-
propylphenol in 2000 parts of toluene is heated to 55 C . with
stirring, and 200 parts (2.5 equivalents) of 50% aqueous
sodium hydroxide solution is added, followed by 1820 parts
(55 equivalents) of paraformaldehyde (over 15 minutes)7
During the paraformaldehyde addition, the temperature rises
to 100C. It is blown with nitrogen and cooled to 85c.,
whereupon 150 parts of acetic acid is added. Water is
removed by azeotropic distillation and the remaining product
is filtered through a filter aid material.
A mixture of 555 parts (1.5 eguivalents) of the inter-
mediate thus obtained, 300 parts of isopropyl alcohol, 100
parts of xylene and 270 parts (3 equivalents) of guanidine
carbonate is heated under reflux for 12 hours. Xylene, 200
parts, is then added and volatiles are removed by distilling
at 110C. The mixture is filtered and the solids are washed
1055051
with xylene; the combined filtrate and washings are vacuum
stripped and 600 parts of mineral oil is added. Stripping
of volatile materials continued and the remaining liquid is
filtered through a filter aid material. The filtrate is the
desired product (48% solution in mineral oil) which contains
3.17% nitrogen.
Example 12
A tetrapropylphenol-formaldehyde intermediate is
prepared by a method similar to that described in Example
11. A mixture of 393 parts (1 equivalent) of that inter-
mediate, 168 parts (2 equivalents) of dicyandiamide, 250
parts of isopropyl alcohol and 458 parts of mineral oil is
heated to reflux and maintained at that temperature for
about 9 hours. Volatiles are then removed by vacuum strip-
ping and the residual liquid is filtered using a filter aid
material. The filtrate is the desired product (50% solution
in mineral oil) containing 4.41~ nitrogen.
Example 13
A mixture of 393 parts (1 equivalent) of the tetra-
propylphenol-formaldehyde intermediate of Example 12, 318
parts l1.63 equi~alents) of disodium iminodiacetate and 400
parts of xylene is heated under reflux for about 18 hours
and is then filtered. The desired product is obtained as
the filtrate (45% soluticn in xylene~ and contains 0.04%
nitrogen.
Example 14
A mixture of 131 parts (0.33 equivalent) of the tetra-
propylphenol-formaldehyde intermediate of Example 12, 41
parts (1 equivalent) of 3,3-iminodipropionitrile and 200
parts of xylene is heated at 120-130C. for 6-1/2 hours and
- 20 -
10550S~
is then stripped of volatile materials under vacuum. The
residual liquid is filtered through a filter aid material
and the material on the filter is washed with 200 parts of
xylene. The combined filtrate and washings are concentrated
to yield an 86% solution in xylene of the desired product,
containing 8.60% nitrogen.
Example 15
The tetrapropylphenol-formaldehyde intermediate of
Example 12 (589 parts, 1.5 equivalents) is heated to 62C.
and 324 parts (4 equivalents) of aminopropyldiethanolamine
is added over 1 hour at 62-89C. The mixture is heated for
1 hour at89-120C. and is then blown with nitrogen as water
is removed by azeotropic distillation. The residual liquid
is heated at 140-162C. for 5 hours as additional water is
removed, and is then cooled and 200 parts of xylene is
added. The liquid is filtered, using a filter aid material,
and the fiItrate is the desired product (71% solution in
xylene) containing 5.76~ nitrogen.
Example 16
A mixture of 2989 parts (7 equivalents) of a poly-
isobutylphenol in which the polyisobutyl substituent has
a molecular weight of about 330, 56 parts (0.7 equivalent)
of 50% aqueous sodium hydroxide solution and 1000 parts of
toluene is heated to 65C. and 254 parts (7.7 equivalents)
of paraformaldehyde is added. The mixture is heated with
stirring at 65-85C. for about 1 hour, and an additional 254
parts (7.7 equivalents) of paraformaldehyde is added.
Heating is continued at 69-76C. for 2 hours, whereupon 42
parts (0.7 equivalent) of acetic acid is added. Volatile
materials are then removed by azeotropic distillation under
- 21 -
105505~
vacuum and the remaining liquid is filtered through a
filter aid material.
To 457 parts (1.5 equivalents) of the intermediate
thus obtained is added 162 parts (2 equivalents) of
aminopropyl-diethanolamine. The mixture is heated under reflux,
with azeotropic removal of water, for about 2 hours and then at
140-160C. for about 8 hours. It is then cooled to 130C.
and 165 parts of mineral oil is added. The remaining
toluene is removed by distillation and the residual liquid
is filtered. The filtrate is the desired product (75%
solution in mineral oil) and contains 4.16~ nitrogen.
Examples 17 to 20 describe the preparation of inter-
mediates for preparing dispersants of this invention ~nd are
carried out, with variations noted in Table A by the
following pxocedure: A mixture of the polybutenyl-substituted
phenol, mineral oil, n-butanol, sodium hydroxide and
paraformaldehyde is heated at 82-87C. for three hours.
Glacial acetic acid is then added and stirred for one-half
houx to provide a mixture containing the desired intermediate.
These intermediates are converted to the desired dispersants
by the means described in Examples 21-28.
- 22 -
10550Sl
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U~ ~1
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. ~ ~ ~ o
0 Q~ ~ ~~r
.
. Q
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I
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t-- 00 ~ O
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~Z
-- 23 --
~)SS051
Example 21
The intermediate prepared in Example 17 is heated to
120C. and 58 parts of o-aminophenol added. The reaction
mixture is heated at 115-140C. for two hours, then strip-
ped to 160C. under vacuum and filtered. The filtrate is
the desired product (60~ solution in mineral oil, containing
0.30% nitrogen).
Example 22
The intermediate prepared in Example 18 is stripped to
100C. under vacuum and filtered to yield 6430 parts of a
65% oil solution of intermediate.
Example 23
The intermediate prepared in Example 22, 970 parts, is
heated to 75C. and 69 parts of sulfanilic acid is added.
The mixture is heated at 160-200C. for 11 hours as water
is removed while blowing with nitrogen. The mixture is
filtered at 150C. to yield the desired product (65% sol-
ution in mineral oil).
Example 24
The intermediate prepared in Example 22, 970 parts, 75
parts of n-butanol and 30 parts of glycine is heated at 170-
175C. for 11 hours as distillate is removed while blowing
with nitrogen. The mix~ure is filtered to yield the desired
product (65% oil solution, containing 0.24~ nitrogen)~
Example 25
The intermediate prepared in Example 17 is heated to
120C. and 56.3 parts of aniline is added~ The reaction
mixture is heated at 155-180C. for 8 hours, then stripped
to 190C. under vacuum and filtered to yield the desired
product (60~ solution in mineral oil, containing 0.34%
nitrogen).
- 24 -
10~50Sl
Ex mple 26
The intermediate prepared in Example 17 is heated at
125C. for 1.5 hours as distillate is removed while blowing with
nitrogen. The reaction mixture is cooled to 70C., and 180
parts of p-aminophenol and 75 parts of n-butanol is added. The
mixture is heated at 148C. for 3 hours and water is removed by
azeotropic distillation, then stripped to 160C~ under vacuum
and filtered. The filtrate is a solution/dispersion product
which contains 40% mineral oil and 0.32% nitrogen.
Example 27
The intermediate prepared in Example 19 is heated to
85C. and 84.5 parts of diphenylamine is added. The reaction
mixture is heated at 150-160C. for 4 hours and water is removed
by azeotropic distillation, then stripped to 160C. under vacuum.
The mixture is filtered to yield the desired product (60%
solution in mineral oil, containing 0.52% nitrogen).
ExamPle 28
The intermediate prepared in Example 20 is heated at
120C. for 1.5 hours as water is removed by a Dean-Stark
trap while blowing with nitrogen. Phenothiazine, 119 parts,
is added and heated at 150-170C. for 5 hours, then stripped
at 170C. under vacuum. The mixture is filtered to yield the
desired product (60~ solution in mineral oil 9 which contains
0.43% nitrogen and 1.07~ sulfur.)
As previously indicated, the compositions of this
invention are useful as additives for lubricants, in which
they function primarily as sludge dispersants and detergents.
Such dispersants and detergents disperse and remove from
surfaces sludge which forms in the lubricant during
use. They can be employed in a variety of lubricants based
D7 - 2~ -
1~
~LOSSOS~
on diverse oils o~ 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 engines, two-cycle engines,
aviation piston engines, marine and railroad diesel engines,
and the like. They can also be used in gas engines, jet
aircraft turbines, stationary power engines and turbines and
the like. Automatic transmission fluids, transaxle lubri-
cants, gear lubricants, metal-working lubricants, hydraulic
fluids and other lubricating oil and grease compositions can
also benefit from the incorporation therein of the composi-
tions 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 oils. Synthetic lubricating oils 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 dipnenyl ethers and alkylated diphenyl
sulfides and the derivatives, analogs and homologs thereof
and the likeO
- 26 -
1055(~51
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
are exemplified by the oils prepared through 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-C8 fatty acid esters, or the
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-ethyl-
hexanoic acïd and the like.
- 27 -
lOS505~
Esters useful as synthetic oils also include those made
from Cs 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 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 O~l~ or more properties. Many such purifi-
cation techniques are known to those of skill in the art
- 28 -
105505~
such as solvent extraction, secondary distillation, acid or
base extraction, filtration, percolation, etc. Rerefined
oils are obtained by processes si~ilar to those used to
obtain refined oils applied to refined oils which have been
already used in service. Such rerefined oils are also knowr.
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 parts (by weight) of the
composition of this invention is dissolved or stably dis-
persed in 100 parts of oil to produce a satisfactory lubri-
cant. The invention also contemplates 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 stabllizers 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 by the
treatment of an olefin polymer ~e.g., polyisobutene having a
molecular weight of lO00) with a phosphorizing agent such as
phosphorus trichloride, phosphorus heptasulfide, phosphorus
pentasulfide, phosphorus trichloride and sulfur, white
phosphorus and a sulfur halide, or phosphorothioic chloride.
The most commonly useJ salts of such acids are those of
sodium, potassium, lithium, calcium, magnesium, strontium
and barium.
- 29 -
~1055051
The term "basic salt" is used to designate metal salts
wherein the metal is present in stoichiometrically larger
amounts than the organic acid radical. The commonly
employed methods for preparing the basic salts involve
heating a mineral oil solution of an acid with a stoichio-
metric excess of a metal neutralizing agent such as the
metal oxide, hydroxide, carbonate, bicarbonate, or sulfide
at a temperature above 50C. and ~iltering 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 include
phenolic substances such as phenol, naphthol r C6 -2 6 alkyl-
phenols, thiophenol, sulfurized alkylphenol, and condensa-
tion products of formaldehyde with a phenolic substance;
-2 o alcohols such as methanol, 2-propanol, octyl alcohol,
cellosolve, carbitol, ethylene glycol, stearyl alcohol, and
cyclohexyl alcohol; and Cl-20 amines such as aniline,
phenylenediamine, phenothiazine, phenyl-b-naphthylamine, and
dodecylamine. A particularly effective method for preparing
the basic salts comprises mixing an acid with an 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.
Ashless detergents and dispersants are so called
despite the fact that, depending on its constitution, the
dispersant may upon combustion yield a non-volatile material
such as boric oxide or phosphorus pentoxide; however, it
does not ordinarily contain metal and therefore does not
yield a metal-containing ash on combustion. Many types are
known in the art, and any of them are suitable for use in
- 30 -
,, ~ .,
lOSSOSl
the lubricants of this invention. The following are illus-
trative:
(1) Reaction products of carboxylic acids (or deriva-
tives thereof) containing at least about 34 and preferably
at least about 54 carbon atoms with nitrogen-containing
compounds such as amines, organic hydroxy compounds such as
phenols and alcohols, and/or basic inorganic materials.
Examples of these "carboxylic dispersants" are described in
British Patent 1,306,529 and in many U.S. Patents, including
the following:
3,163,603 3,351,552 3,541,012
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 3,632,510
3,311,558 3,451,933 3,632,511
3,316,177 3,454,607 3,697,428
3,340,281 3,467,668 3,725,~41
3,341,542 3,501,405 Re 26,433
3,346,493 3,522,179
(2) Reaction products of relatively high molecular
weight aliphatic or alicyclic halides with amines, prefer-
ably polyalkylene polyamines. These may be characterized as
"amine dispersants" and examples thereof are described, for
example, in the following U.S. Patents:
3,275,554 3,454,555
3,438,757 3,565,804
- 31 -
l.OSS051
(3) Products obtained by post-treating the carboxylic
or amine dispersants with such reagents as urea, thiourea,
carbon disulfide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, nitriles,
epoxides, boron compounds, phosphorus compounds or the like.
Exemplary materials of this kind are described in the
following U.S. Patents:
3,036,003 3,367,943 3,579,450
3,087,936 3,373,111 3,591,598
3,200,107 3,403,102 3,600,372
3,216,936 3,442,808 3,639,242
3,254,025 3,455,831 3,649,229
3,256,185 3,455,832 3,64g,659
3,278,550 3,493,520 3,658,836
3,280,234 3,502,677 3,697,574
3,281,428 3,513,093 3,702,757
3,282,955 3,533,945 3,703,536
3,312,619 3,539,633 3,704,308
3,366,569 3,573,010 3,708,522
(4) Interpolymers of oil-solubilizing monomers such as
decyl methacrylate, vinyl decyl ether and high molecular
weight olefins with monomers containing polar substituents,
e.g., aminoalkyl acrylates or acrylamides and poly-(oxy-
ethylene)-substituted acrylates. These may be characterized
as "polymeric dispersants" and examples thereof are dis-
closed in the following U.S. Patents:
3,3~9,658 3,666,730
3,449,250 3,687,849
3,519,565 3,702,300
, ..
- 32 -
105SOSl
The pertinent disclosures of all of the above-noted
patents are incorporated by reference herein.
Extreme pressure agents and corrosion-inhibiting and
oxidation-inhibiting agents are exemplified by chlorinated
aliphatic hydrocarbons such as chlorinated wax; organic
sulfides and polysulfides such as benzyl disulfide, bis-
(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized
methyl ester of oleic acid, sulfurized alkylphenol, sul-
furized dipentene, and sulfurized terpene; phosphosulfurized
hydrocarbons such as the reaction product of a phosphorus
sulfide with turpentine or methyl oleate; phosphorus esters
including principally dihydrocarbon and trihydrocarbon
phosphites such as dibutyl phosphite, diheptyl phosphite,
dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl
phenyl phosphite, tridecyl phosphite, distearyl phosphite,
dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite,
polypropylene (molecular weight 500)-substituted phenyl
phosphite, diisobutyl-substituted phenyl phosphite; metal
thiocarbamates, such as zinc dioctyldithiocarbamate,
and barium heptylphenyl dithiocarbamate; Group II metal
phosphorodithioates such as zinc dicyclohexylphosphorodi-
thioate, zinc dioctylphosphorodithioate, barium di(heptyl-
phenyl)phosphorodithioate, cadmium dinonylphosphorodithio-
ate, 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 fuel compositions of the present invention contain
a major proportion of a normally liquid fuel, usually a
hydrocarbonaceous petroleum distillate fuel such as aviation
~055051
or motor g~soline as defined by ASTM Specification D-439-73
and diesel fuel or fuel oil as defined by ASTM Specification
D-396. No~mally 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
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~ distilla-
tion point.
Generally, these fuel compositions contain an amount of
the compositions of this invention sufficient to impart
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 composi~
tions generally exhibit excellent engine oil sludge dis-
persancy and detergency properties. In addition, they
exhibit anti-rust and carburetor/fuel line deposit-removing
and deposit-inhibiting properties.
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 ~an include anti-knock agents such as tetra-alkyl lead
- 34 -
1055051
compounds, lead scavengers such as halo-alkanes (e.g.g
ethylene dichloride and ethylene dibromide) J deposit preventors
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 invention
are combined with other ashless dispersants in gasoline.
Such ashless dispersants are preferably esters of a mono- or
polyol and a high molecular weight mono- or polycarboxylic
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, o55,337 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, to which reference may
be made for further details of suitable esters and methods for
their preparation. ~enerally, 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 addi~ives are combined with Mannich condensation
. .,
-
~055051
products formed from substituted phenols, aldehydes, poly-
amines, and amino pyridines. 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 inven~ion can be added directly
to the fuel or lubricating oil to form the fuel and lubri-
cant compositions of this invention or they can be diluted
with a 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 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-
described ashless dispersants in the aforesaid proportions.
The remainder of the concentrate is the solvent/diluent.
Typical fuel and luhricating compositions of this
invention are listed in Tables I and II, respectively.
Except for the values for mineral oil and for the products
of Examples 2, 5, 7, 9 and 11, all amounts are exclusive of
mineral oil used as diluent. In Table I, amounts are in
parts by weight per million parts of gasoline~
- 36 -
10550Sl
TABLE I
Parts by weight per
million parts gasoline
Ingredient Fuel A B
Product of Example 5 98 -~
Product of Example 9 -- 150
B Tretolite proprietary demulsifier
composition -- 2
Exxon proprietary demulsifier
composition -- 4
Nalco proprietary demulsifier
composition -- 2
Xylene -- 74
Isooctyl alcohol -- 49
ks
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~ossos~
T~BLE II
Parts by weight
Ingredient Lubricant C D E
Mineral Oil (SAE 10W-40 base) 78.18 -- 80.08
Mineral oil tSAE 30 base) -- 90.69 __
Product of Example 2 4.44 -- --
Product of Example 7 -- 5,00 --
Product of Example 11 -- -- 2.00
Polyisobutenyl succinic anhydride-
polyethylene polyamine reaction
product -- -- 1.89
Polyisobutenyl succinic anhydride-
polyethylene polyamine-boric
acid reaction product 2.04 -- --
Pentaerythritol ester of poly-
isobutenyl succinic acid -- -- 1.77
Basic calcium petroleum sulfonate -- 0.57 --
Basic calcium salt of alkyl-
phenol sulfide -- 1.6~ --
Zinc tetrapropenylphenylphos-
phorodithioate -- 2.05 --
Tetrapropenylsuccinic acid 0.34 -- --
- Reaction product of alkylphenol,
formaldehyde and dimer-
captothiadiazole 0 49 ~~ ~~
Sulfurized Diels-Alder adduct 1.33 -- 1.31
2,6-Di-t-~utyl-p-cresol 0.03 -- 0.03
Hindered phenol antioxidant 0.32
Ethylene-propylene-diene
terpolymer 12.49 -- 12.57
Vinyl carboxylate-vinyl ~ther-
dialkyl fumarate terpolymer 0.34 -- 0.35
Silicone anti-foam agent 0.006 0.01 0.co~
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lOSS051
SUPPLEMENTARY DISCLOSURE
In further embodiments of the invention described in
the principal disclosure, the hydrocaxbon-based carbonyl
compound that is employed as the said second reagent comprises
a ketone. Mixtures of ketones with aldehydes can also be
used as the second reagent. Suitable ketones include
acetone, methyl ethyl ketone, acetophenone, benzophenone
and the like. In general the carbonyl compounds are of the
formula RC(O)R wherein each R is independently hydrogen or
a lower hydrocar~on-based group. Typically each R is inde-
pendently hydrogen or a Cl-7 hydrocarbyl group.
The intermediates that are obtained by reaction of the
first and second reagents can thus be xepresented by the
formulae
(IH)l 2 (OH)l_~
Ar(CR20H) and/or HO ~ CR2ArCR20 ~x H
wherein R, Ar, and x are as defined in the principal dis~
closure.
These intermediates are then employed to make the
nitrogen-aontaining compositions as described in the princi-
pal disclosure.
The hydrocarbon-based substituent R of the aromatic
moiety Ar mQy be dexived from homo- or interpolymers of a
C2 8 1- no- or di-olefin such as ethylene, propylene, the
various butenes, butadiene, allylene, styrene, isoprene and
the like.
In preferred embodiments, the hydrocarbon-based sub-
stituènt R' may generally oontain an average of up to about
700, typically up to about 400, carbon atoms. In more
preferred forms, R' is derived from polypropylene or poly-
- 39 ~
lOSSOSl - 4(' -
butene and has an average of about 50 to about 400 carbon
atoms.
A particular preferred class of intermediates that
are prepared in the first step of the reaction are those
made from para-substituted phenols and having the general
formulae:
OH C ~ 0~ ~ OH
~ ~ and
R'
wherein R' is an alkyl or alkenyl group of about 30 to about
400 carbons and x is an integer of 1 to about 10. Exemplary
of R' in these preferred intermediates are those made from
polybutenes. These polybutenes are usually obtained by
polymerization of a C4 refinery stream having a butene
content of 35 to 75 weight percent and isobutene content of
30 to 60 weight percent in the presence of a Lewis acid
catalyst such as aluminum trichloride or boron trifluoride.
They contain predominantly (greater than 80~ of total
repeat units) isobutylene repeating units of the configuration
IH3
CH2 C
CH3
In otherpreferred intermediates, the R' is derived from a
polypropylene polymer or an ethylene/propylene interpolymer
oontaining an appropriate number of carbon atoms.
In carrying out the reaction described in the principal
disclosure, the intermediate that is formed in the first step
is usually substantially neutralized before proceeding to the
step o reaction with the amino compound. The neutralization
lOS~VSl
is~ however, an optional step and is not, always employed.
A preferred group of amino compounds consists of poly-
amines, especially alkylene polyamines conforming ~or the
most part to the formula
H-N ~ alkylene-N )n A
A A
wherein n is an integer of 1 to about 10, each A is independ-
ently a hydrocarbon-based substituent or hydrogen atom,
preferably a lower alkyl group or a hydrogen atom, and the
alkylene radical is preferably a lower alkylene radical
of up to 7 carbon atoms. Mixtures of such polyamines are
similarly useful. In certain instances, two A groups on the
same amino nitrogen can be combined together, sometimes
through a nitrogen atom and othe~ times through carbon-to-
carbon bonds to form a five or six membered ring including
the ami~o nitrogen, two A groups and, optionally, oxygen
or nitrogen. Examples of amines wherein two A groups are
combined to form a ring include ~-aminoethyl morpholine,
N-3-aminopropyl-pyrrolidine, etc.
Some embodiments of the invention æ e illustrated in
the following Examples. All parts are by weight and all
lecular weights are determined by V.PØ unless otherwise
indicated.
Example ?9
Example 29 is carried out in essentially the same manner
as Example 1, except that the l-buta 1 solvent/diluent is
omitted and the mineral oil solvent/diluent is replaced by
an equal amount of xylene. Filtration of the final product
at 100-90C./170 torr through filter aid provides a xylene
- 41 -
lOS5051
solution of the desired f:inal product which contains 39.4
xylene and is useful as an additive for gasoline.
Example 30
A mixture of 450 parts of a polypropylene-substituted
phenol (the polypropylene substituent having a Mn = 860), 25
parts para~ormaldehyde and 3 parts of 50~ aqueous NaOH, 100
parts of xylene and 25 parts normal butanol is heated at 80-
90C. for 3 h~urs. Then 2.3 part~ of glacial aceti~ acid is
added to neutralize the intermediate mixture. The poly-
ethylene polyamine described in Example 1 (45 parts) isadded and the mixture is heated to 160C. for 5 hours while
distillate c~llects. The mixture is stripped at 165C./15
torr and filtered to provide as a filtrate the desired
product containing 2.98% nitrogen.
Tb this solution is added 344 parts of the oommercial
polyethylene polyamine mixture described in ~xample 1.
The mixture is heated from 88C. to 120C. over 1.5 hours, from
120-150C. over 1.25 hours, and 150-155C. over 4.5 hours.
The mixture is then heated from 155-157C. for 5 hours while
a slow stream of nitrogen is passed through it. Approximately
250 parts of distillate is collected from the mixture. The
mixture is stripped to 150C./10 torr and the residue fil
tered at that temperature to provide an oil solution of
desired product containing 4 ~ oil and 1.58~ nitrogen~
The pr~ducts of Examples 29 and 30 can be used in the
same manner as the products of Examples 1 to 28.
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